EP0918083B1 - Utilisation de dérivés du dithioéthylène en tant qu'agents améliorant la compatibilité avec les élastomers fluorocarbonés - Google Patents

Utilisation de dérivés du dithioéthylène en tant qu'agents améliorant la compatibilité avec les élastomers fluorocarbonés Download PDF

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Publication number
EP0918083B1
EP0918083B1 EP97309298A EP97309298A EP0918083B1 EP 0918083 B1 EP0918083 B1 EP 0918083B1 EP 97309298 A EP97309298 A EP 97309298A EP 97309298 A EP97309298 A EP 97309298A EP 0918083 B1 EP0918083 B1 EP 0918083B1
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Prior art keywords
carbon atoms
oil
thirty carbon
use according
lubricating oil
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EP97309298A
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German (de)
English (en)
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EP0918083A1 (fr
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Pierre Tequi
Jacques Cazin
Andrew W. Ho
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Chevron Phillips Chemical Co LP
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Chevron Oronite Co LLC
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    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/062—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Definitions

  • the present invention relates to an inhibitor as an additive in lubricants to improve the compatibility with fluorocarbon elastomers.
  • Applications can be in automotive engine oils, automotive transmission oils, specialty industrial oil packages, and the like.
  • This invention relates to the improvement of the compatibility of a lubricating oil composition comprising dispersants containing basic nitrogen atoms, with fluorocarbon elastomer seals.
  • Lubricating oil formulations particularly for the automotive industry, make use of a large number of additives, each having its respective role.
  • the most important additives include detergents and dispersants, which, as their names indicate, are used to guarantee engine cleanliness and to keep in suspension the impurities produced in particular by the attack of the metallic or other parts of engines by the lubricating oil formulation.
  • the most widely used dispersants today are products of the reaction of succinic anhydrides substituted in the alpha positon by an alkyl chain of the polyisobutylene type (PIBSA) with a polyamine, possibly post-treated with a derivative of boron, ethylene carbonate or other post-treatment reagents known in the specialized literature.
  • polyamines used polyalkylene-amines are preferred, such as diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA) and heavier poly-alkylene-amines (HPA).
  • polyamines react with the succinic anhydrides substituted by alkyl groups of the polyisobutylene type (PIBSA) to give, according to the molar ratio of these two reagents, mono succinimides, bissuccinimides, or mixtures thereof.
  • PIBSA polyisobutylene type
  • reaction products possibly post-treated, generally have a basic nitrogen content of from 5 to 50, as measured by the base number or BN, expressed as mg KOH/g sample. This enables them to protect the metallic parts of an engine while in service from corrosion by acidic components formed as a result of the oxidation of the lubricating oil or the fuel, while keeping these oxidation products dispersed in the lubricating oil to prevent their agglomerization and their deposition in the casing containing the lubricating oil formulation.
  • dispersants are even more effective if their relative basic nitrogen content is high, that is, insofar as the number of nitrogen atoms of the polyamine is larger than the number of succinic anhydride groups substituted by polyisobutenyl.
  • the lubricating oil formulations must contain many other ingredients, each of which has a very specific role.
  • detergents such as sulphonates, alkylphenates or metallic salicylates, sulphurized or not, anti oxidants, particularly zinc dialkyl dithiophosphates, antiwear and extreme pressure agents, foam inhibitors, friction reducers, rust inhibitors, corrosion inhibitors, pour point depressants, viscosity index improvers and many other additives.
  • the present invention is based upon our unexpected discovery that certain dithioethylene derivatives, which are useful as an antiwear and/or extreme pressure additive in lubricating oil compositions, as demonstrated in U.S. Patent No. 5,641,735, also provides improved compatibility with fluorocarbon elastomer seals in the Volkswagen PV 3344 test. They are effective from about 0.1 weight % treat rate, preferably about from 0.1 to 1.5 weight %, providing excellent compatibility with fluorocarbon elastomer seals, while yielding engine wear protection.
  • the dithioethylene derivatives are of the formula: wherein R and R 1 are independently alkoxycarbonyl having four through thirty carbon atomsalkenyloxycarbonyl having eight through thirty carbon atoms, or aryloxycarbonyl having seven through thirty carbon atoms;
  • R 2 and R 3 are independently sulfurized alkyl having three through thirty carbon atoms and at least one sulfur atoms, alkoxycarbonylalkyl wherein the alkoxy moiety has two through five carbon atoms and the alkyl moiety has one through ten carbon atoms; arylalkyl having seven through thirty carbon atoms, or borated hydroxyalkyl having two through thirty carbon atoms, with the proviso that R, R 1 , R 2 and R 3 together contain sufficient carbon atoms to render the compound oil soluble in an oil of lubricating viscosity.
  • R and R' are independently alkoxycarbonyl having eight through thirty carbon atoms.
  • R and R 1 are each (saturated or unsaturated) carbo-2 - ethylhexoxy and R 2 and R 3 are borated hydroxyalkyls having two through thirty carbon atoms.
  • R 2 and R 3 share a common boron atom, forming a cyclic structure.
  • oil solubility is generally provided by the total number of carbon atoms in the R, R 1 , R 2 and R 3 substituents.
  • oil solubility is provided by increasing the chain length or number of carbon atoms of the other substituents.
  • a lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a fluorocarbon elastomer compatibility improving agent of the present invention, may be formed.
  • a concentrate composition comprising about from 0.5 to 30 weight % of a fluorocarbon elastomer compatibility improving agent of the present invention and an inert hydrocarbon liquid diluent, may be formed.
  • the present invention involves the unexpected discovery that a novel genus of compounds which is useful as antiwear and/or extreme pressure additive in lubricating oil compositions also provides improved compatibility with fluorocarbon elastomer seals in the Volkswagen PV 3344 test .
  • R and R' are independently alkoxycarbonyl having eight to thirty carbon atoms.
  • R substituent is identical to the R 1 substituent, more preferably both R and R 1 are alkoxycarbonyl, most preferably both R and R 1 are carbo-2-ethylhexoxy.
  • both R 2 and R 3 are borated hydroxyalkyl having two through thirty carbon atoms.
  • R 2 and R 3 share a common boron atom, forming a cyclic structure.
  • alkyl refers to both straight- and branched chain alkyl groups and includes primary, secondary and tertiary alkyl groups.
  • alkenyl refers to an alkyl group with unsaturation.
  • aryl refers to a substituted phenyl group.
  • alkylcarbonyl refers to the group wherein R' is alkyl.
  • alkenylcarbonyl refers to the group wherein R' is alkenyl.
  • arylcarbonyl refers to the group wherein R' is aryl.
  • alkoxycarbonyl refer to the group wherein R' is alkyl.
  • alkenyloxycarbonyl refer to the group wherein R' is alkenyl.
  • aryloxycarbonyl refer to the group wherein R' is aryl.
  • alkoxycarbonylalkyl refers to the group wherein R' and R" are alkyl.
  • arylalkyl refers to an alkyl group substituted with an aryl group.
  • hydroxyalkyl refers to an alkyl group substituted with an hydroxyl group.
  • borated hydroxyalkyl refers to the reaction product of a hydroxyalkyl with boric acid.
  • Carbocycle refers to a saturated cyclic group with a carbon skeleton.
  • sulfurized alkyl refers to an alkyl group that has been substituted with sulfur.
  • Base Number refers to the amount of base equivalent to milligrams of KOH in 1 gram of sample. Thus, higher BN numbers reflect more alkaline products and therefore a greater alkalinity reserve.
  • the BN of a sample can be determined by ASTM Test No. D2896 or any other equivalent procedure.
  • oil solubility means that the additive has a solubility of at least 50 grams per kilogram and preferably at least 100 grams per kilogram at 20° C in a base lubricating oil.
  • oil of lubricatina viscosity generally refers to an oil having a viscositv of 3 ⁇ 10 -6 to 2-0 ⁇ 10 -5 m 2 /s (3-20 cSt) at 100° C in the case of lubricating oil compositions and may be a single oil or a blend of oils.
  • the compounds of the present invention can be prepared by adapting the procedures described in U.S. Patent Nos. 4,389,400 and 4,447,450, by employing the appropriate starting materials corresponding to the substituent desired in the compounds of the present invention.
  • R 2 is identical to R 3
  • R 1 and R 2 are as defined herementioned
  • X is halide, preferably chloride or bromide, or any alkylating agent with a suitable leaving group
  • M is a metal cation, preferably an alkali metal, for example potassium or ammonium cation.
  • Also although M is shown as a monovalent cation for the sake of simplicity, M could also be a divalent or polyvalent cation, in which case M would be represented as M/r wherein r is the valence of M).
  • This process can be conveniently effected by contacting Compound (A) with Compound (B), under reactive conditions, preferably in an inert organic solvent.
  • the process is conducted at temperatures in the range of about from -10° C to 50° C, preferably about from 20° to 40° C, for about from 1 to 48 hours, preferably about from 4 to 8 hours, using about from 2 to 4 moles, preferably about from 2 to 2.2 moles, of (B) per mole of Compound (A).
  • Suitable inert organic solvents which can be used include, for example, dioxane, tetrahydrofuran, dimethylformamide, toluene, methanol, and compatible mixtures thereof.
  • the first step in this process can be conveniently effected by contacting compound A' with an inorganic base (e.g. potassium hydroxide) and carbon disulfide under reactive conditions, preferably in an inert organic solvent.
  • an inorganic base e.g. potassium hydroxide
  • carbon disulfide under reactive conditions, preferably in an inert organic solvent.
  • this process step (2) is conducted at temperatures in the range of about from 0° to 50° C, preferably about from 0° to 20° C, for about from 1 ⁇ 2 to 4 hours, preferably about from 1 to 2 hours, using about from 2 to 3 equivalents, preferably about from 2 to 2.1 equivalents, inorganic base and about from 1 to 2.5 equivalents of carbon disulfide per mole of Compound (A').
  • Suitable inert organic bases and inert organic solvents that can be used include those already described above.
  • Suitable inorganic bases include, for instance, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
  • the reaction employs pulverized potassium hydroxide as the base in a dimethylformamide medium.
  • the compounds of Formulas (A') are generally known compounds and can be prepared by known procedures or by obvious modifications thereof (e.g., by using appropriately substituted starting materials).
  • the next reaction step (3) can be conveniently effected by contacting compound (C) with the appropriate organic halide (B) having the desired R 2 substituent, under reactive conditions, preferably in an inert organic solvent.
  • This step of this process is typically conducted at temperatures in the range of about from 0° to 100° C, preferably about from 20° to 80° C, for about from 1 to 26 hours, preferably about from 4 to 8 hours, using about from 1 to 2 moles, preferably about from 1 to 1.1 moles of compound (B) per mole of compound (C).
  • Suitable inert organic solvents which can be used include, for example, those described with respect to reaction equation (1) used to make compounds (I'), and the like.
  • the last reaction step (4) can be effected by contacting compound (D) with inorganic base and compound (B') under reactive conditions, preferably in an inert organic solvent, and is conveniently conducted in situ with the reaction product mixture of the previous reaction step (3) without removal of the organic solvent.
  • Process reaction step (4) is typically conducted at temperatures in the range of about from 0° to 100° C, preferably about from 20° to 80° C, for about from 1 to 26 hours, preferably about from 4 to 8 hours, using about from 1 to 2 equivalents, preferably about from 1 to 1.1 equivalents, of inorganic base and about from 1 to 2 equivalents, preferably about from 1 to 1.2 equivalents, of compound (B') per compound (D).
  • Suitable inert organic bases and inert organic solvents that can be used include those already described above.
  • the starting materials of formula A can be prepared by the same general procedure as reaction step (2) by increasing the amount of inorganic base to produce the bis salt instead of the mono-salt: wherein R, R 1 and M are as defined hereinabove.
  • Reaction step (5) can be conveniently conducted by adding about from 2 to 2.5 equivalents of an inorganic base to the appropriate reagent A'.
  • the reaction is done in the liquid phase employing an inert organic solvent. Suitable inert organic bases and inert organic solvents that can be used include those already described above.
  • the reaction employs pulverized potassium hydroxide as the base in a dioxane medium.
  • About from 1 to 2.5 equivalents of carbon disulfide is then added to the system.
  • the reaction is generally conducted at about from 0° to 100° C, although preferably at about from 5° to 40° C, and is generally completed from within about from 1 to 24 hours. In some instances it may be convenient to conduct reaction step in situ with the reaction product mixture produced by step (5) without removal of the solvent.
  • Reaction steps (2), (4) and (5) involve the addition of a solid base to an organic solvent.
  • a phase-transfer catalyst is preferably employed in these reactions to aid in the transfer of the solid base into the organic solvent.
  • Preferred catalysts include, for instance, tetraalkylammonium halides.
  • a particularly preferred catalyst is tetra-n-butylammonium bromide.
  • about 0.025 equivalents of the catalyst have been found sufficient to accomplish the catalytic effect desired.
  • a phase-transfer catalyst is useful to facilitate transfer from the aqueous phase to the organic phase.
  • Reactions (3) and (4) involve adding a metallic salt (preferably potassium thiolate) to an organic medium.
  • a catalytic amount for example about 0.025 equivalents
  • Catalysts such as tetraalkylammonium halide salts are generally preferred.
  • Suitable bases which can be used include those already described above.
  • Suitable phase transfer agents are agents which transfer hydrophilic ions into a lipophilic organic medium and include, for example, benzyl triethylammonium chloride, tetra-n-butylammonium chloride, methyltrioctylammonium chloride, tetra alkylphosphonium halides, and the like.
  • the compounds of formula I, wherein R 2 and R 3 are sulfurized alkyl can also be conveniently prepared by first preparing the desired R 2 , R 3 olefin of formula I and reacting this compound with the desired amount of sulfur.
  • Such sulfurization procedures are known to the art and generally involve contacting an olefin with powdered or liquid sulfur, or a sulfur equivalent, e.g. SCl 2 , under reactive conditions at temperatures in the range of about from 80° to 110° C, typically in an inert organic solvent such as toluene.
  • the reactions described above are conducted as liquid phase reaction and hence pressure is generally not significant except as it affects temperature (boiling point) where reactions are conducted at reflux. Therefore, these reactions are generally conducted at pressures of about from 300 to 3,000 mm of mercury and conveniently are conducted at about atmospheric or ambient pressure.
  • reaction temperatures e.g., reaction temperatures, times, mole or equivalent ratios of reactants, solvents, etc.
  • Optimum reaction conditions e.g., temperature, reaction time, mole ratios, solvents, etc.
  • Lubricating oil compositions can be conveniently prepared by simply blending or mixing of the compound(s) of formula I and/or an oil soluble salt thereof with an oil of lubricating viscosity (base oil).
  • base oil oil of lubricating viscosity
  • the compounds of the invention may also be preblended as a concentrate or package with various other additives in the appropriate ratios to facilitate blending of a lubricating oil composition containing the desired concentration of additives.
  • the compounds of the present invention can be blended with base oil a concentration at which they provide provides improved compatibility with fluorocarbon elastomer seals and are both soluble in the oil and compatible with other additives in the desired finished lubricating oil.
  • Compatibility in this instance generally means that the present compounds as well as being oil soluble in the applicable treat rate also do not cause other additives to precipitate under normal conditions.
  • Suitable oil solubility/compatibility ranges for a given compound of lubricating oil formulation can be determined by those having ordinary skill in the art using routine solubility testing procedures. For example, precipitation from a formulated lubricating oil composition at ambient conditions (about from 20° to 25° C) can be measured by either actual precipitation from the oil composition or the formulation of a "cloudy" solution which evidences formation of insoluble wax particles.
  • the lubricating oil composition contains about from 0.05 weight % to 5 weight %, preferably about from 0.1 weight % to 2 weight % based on the total weight of the composition, of a fluorocarbon elastomer compatibility improving agent selected from the lubricating oil soluble compounds of formula I and mixtures thereof. More preferably, the lubricating oil composition contains about from 0.2 to 1.5 weight % of the said fluorocarbon elastomer compatibility improving agent.
  • the lubricating oil, or base oil, used in the lubricating oil compositions are generally tailored to the specific use e.g. automotive engine oils, automotive transmission oils, specialty industrial oil packages, etc.
  • the base oil typically will be a mineral oil or synthetic oil of viscosity suitable for use in the crankcase of an internal combustion engine such as gasoline engines and diesel engines.
  • the lubricating oils may be derived from synthetic or natural sources.
  • Mineral oil for use as the base oil includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
  • Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
  • Useful synthetic hydrocarbon oils include liquid polymer of alpha olefins having the proper viscosity.
  • the hydrogenated liquid oligomers of C 6 to C 12 alpha olefins such as 1-decene trimer.
  • alkyl benzenes of proper viscosity such as didodecyl benzene can be used.
  • Useful synthetic esters include the esters of both monocarboxylic acid and polycarboxylic acids as well as monohydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and the like.
  • Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used.
  • Blends of various mineral oils, synthetic oils and minerals and synthetic oils may also be advantageous, for example to provide a given viscosity or viscosity range.
  • the base oils or base oil mixtures for engine oil are preselected so that the final lubricating oil, containing the various additives, including the present fluorocarbon elastomer compatibility improving agent, has a viscosity at 100° C of about from 4 ⁇ 10 -6 to 2 ⁇ 2 ⁇ 10 -5 m 2 /s (4 to 22 centistokes), preferably from about 1 ⁇ 10 -5 to 1 ⁇ 7 ⁇ 10 -5 m 2 /s (10 to 17 centistokes) and more preferably from about 1 ⁇ 3 ⁇ 10 -5 to 1 ⁇ 7 ⁇ 10 -5 m 2 /s (13 to 17 centistokes).
  • the lubricating oil composition will contain a variety of compatible additives desired to impart various properties to the finished lubricating oil composition depending on the particular end use and base oils used.
  • additives include neutral and basic detergents (such as natural and overbased organic sulfonates and normal and overbased phenates and salicylates), dispersants, ashless dispersants (such as various polyalkylsuccinimides or polyalkylsuccinic acid esters), wear inhibitors (such as zinc dialkyl dithiophosphates), rust inhibitors, foam inhibitors, pour point depressants, antioxidants, viscosity index (VI) improvers, and dispersant VI improvers.
  • neutral and basic detergents such as natural and overbased organic sulfonates and normal and overbased phenates and salicylates
  • dispersants such as various polyalkylsuccinimides or polyalkylsuccinic acid esters
  • wear inhibitors such as zinc dialkyl dithiophosphates
  • the compounds of the present invention may also be utilised in an additive package or concentrate which may be added to an oil of lubricating viscosity either as the sole additive or in combination with other additives.
  • the additive package will not contain a viscosity index improver because even where desired the viscosity index improver is generally added to the base oil by the lubricant formulator.
  • a preferred additive concentrate contains about from 0.5 to 30 weight %, more preferably about from 1 to 20 weight % of the fluorocarbon elastomer compatibility improving agent of the present invention; sufficient ashless dispersant to provide adequate dispersancy; and about from 90 to 10 weight % of a diluent oil or other compatible inert organic liquid diluent.
  • the concentrate will also frequently contain about from 10 to 60 weight % of various other additives considered desirable from the intended use.
  • a suitable lubricating oil composition would contain
  • a lubricating oil composition can be produced by blending together a major amount of a base oil of lubricating viscosity, about from 1 to 20 weight % of at least one ashless dispersant, from 0 to about 20 weight % of at least one detergent, about from 0.05 to 5 weight % of at least one zinc dithiophosphate, from 0 to about 10 weight % of at least one oxidation inhibitor, from 0 to about 1 weight % of at least one foam inhibitor, from 0 to about 20 weight % of at least one viscosity index improver; and about from 0.05 to 5 weight % of at least one fluorocarbon elastomer compatibility improving agent of the present invention.
  • the lubricating oil composition produced by that method might have a slightly different composition, as components interact.
  • ppm refers to part per million.
  • a mixture (suspension) of1010 g (2.05 mole) of 1,1-Bis(2-hydroxyethylthio)-2,2-bis(carbo-2-ethylhexoxy)ethylene and 253 g (4.1 moles) of Boric Acid was stirred in 2500 ml of Toluene in a 5L flask equipped with a Dean Stark Trap and condenser and under Nitrogen Blanket. The mixture was heated to 95° C and stirred vigorously for 3 hours. The mixture was then heated to reflux (108-115° C) and water was collected from the azeotropic fraction (72 ml in 5 hr.). The mixture was then cooled and filtered to remove excess Boric Acid.
  • the title compounds of Examples 1-4 were respectively formulated into two separate finished lubricating oils, at concentrations of 0.2 weight %, 0.5 weight %, and 1.0 weight %.
  • the finished lubricating oils contained amounts of ashless dispersants typical of a passenger car engine oil, and small amounts of standards detergents, zinc dithiophosphates, oxidation and foam inhibitors, standard viscosity index improvers and base oils of lubricating viscosity to simulate commercial finish lubricating oils.
  • the tested compounds improved the tensile strength at break (TSB), improved the elongation at break (ELB), and produced less cracks on the elastomer dumbbell.
  • the formulations were also evaluated in a laboratory bench test called the blotter spot test.
  • the tested compounds did not have any detrimental effect on the dispersant credit of the dispersant/inhibitor package, measured by that blotter spot test.
  • This paper chromatography technique measures the ability of the candidate lubricating oil to maintain artifical contaminates in suspension. The metric is a rating of degree of dispersion for six different spots, leading to a rating of up to 600, . The higher the number, the better the dispersant credit.
  • the results for the PV 3344 test and the blotter spot test are reported in Table 1 (first fully formulated oil) and Table 2 (second fully formulated oil).
  • Example 5 the title compounds of Examples 1-4 were respectively formulated into two separate finished lubricating oils, as in Example 5, except that the finished lubricating oils contained amounts of ashless dispersants typical of a high performance diesel oil (HPDO) and a super high performance diesel oil (SHPDO), instead of a passenger car engine oil. Formulations were also made at the 1.5 weight % concentration.
  • HPDO high performance diesel oil
  • SHPDO super high performance diesel oil

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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 (7)

  1. Utilisation d'une quantité efficace d'un composé ayant la formule :
    Figure 00270001
    pour améliorer la compatibilité avec des joints d'étanchéité à base d'élastomère fluorocarboné d'une formulation d'huile lubrifiante comprenant des dispersants contenant des atomes d'azote basique,
       dans laquelle R et R1 sont indépendamment :
    (a) un groupe alcoxycarbonyle ayant de quatre à trente atomes de carbone,
    (b) un groupe alcényloxycarbonyle ayant de huit à trente atomes de carbone,
    (c) un groupe aryloxycarbonyle ayant de sept à trente atomes de carbone,
       R2 et R3 sont indépendamment :
    (d) un groupe alkyle sulfuré ayant de trois à trente atomes de carbone et au moins un atome de soufre,
    (e) un groupe alcoxycarbonylalkyle dans lequel le fragment alcoxy a de deux à cinq atomes de carbone et le fragment alkyle a de un à dix atomes de carbone ;
    (f) un groupe arylalkyle ayant de sept à trente atomes de carbone ou
    (g) un groupe hydroxyalkyle boré ayant de deux à trente atomes de carbone,
       avec la condition que R, R1, R2 et R3 ensemble contiennent suffisamment d'atomes de carbone pour rendre le composé soluble dans l'huile dans une huile ayant une viscosité lubrifiante.
  2. Utilisation selon la revendication 1, dans laquelle R et R1 sont indépendamment un groupe alcoxycarbonyle ayant de huit à trente atomes de carbone.
  3. Utilisation selon la revendication 2, dans laquelle le substituant R est identique au substituant R1.
  4. Utilisation selon la revendication 3, dans laquelle R et R1 sont chacun un groupe carbo-2-éthylhexoxy.
  5. Utilisation selon la revendication 2, 3 ou 4, dans laquelle le substituant R2 est identique au substituant R3.
  6. Utilisation selon la revendication 5, dans laquelle R2 et R3 sont des groupes hydroxyalkyle borés ayant de deux à trente atomes de carbone.
  7. Utilisation selon la revendication 6, dans laquelle R2 et R3 partagent un atome de bore commun, formant une structure cyclique.
EP97309298A 1997-11-19 1997-11-19 Utilisation de dérivés du dithioéthylène en tant qu'agents améliorant la compatibilité avec les élastomers fluorocarbonés Expired - Lifetime EP0918083B1 (fr)

Priority Applications (2)

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DE69732486T DE69732486T2 (de) 1997-11-19 1997-11-19 Verwendung von Dithioethylen-Derivaten als Additiv zur Verbesserung der Kompatibilität mit den Fluorokohlenstoffelelastomeren
EP97309298A EP0918083B1 (fr) 1997-11-19 1997-11-19 Utilisation de dérivés du dithioéthylène en tant qu'agents améliorant la compatibilité avec les élastomers fluorocarbonés

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EP97309298A EP0918083B1 (fr) 1997-11-19 1997-11-19 Utilisation de dérivés du dithioéthylène en tant qu'agents améliorant la compatibilité avec les élastomers fluorocarbonés

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006272A (en) * 1980-03-24 1991-04-09 Mobil Oil Corporation Friction reducing additives and compositions thereof
CA1208208A (fr) * 1982-05-07 1986-07-22 Kirk E. Davis Compositions a base d'olefine sulfuree
US5205948A (en) * 1988-08-03 1993-04-27 Mobil Oil Corp. Sulfurized olefin-glycerol monooleate adducts and lubricant compositions containing same
GB2292747B (en) * 1994-08-26 1998-09-16 Exxon Research Engineering Co Lubricant composition containing copolymer to improve seal compatability
US5641735A (en) * 1995-06-06 1997-06-24 Chevron Chemical Company Bis(thio)ethylene ashless wear inhibitors and lubricating oils

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility

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EP0918083A1 (fr) 1999-05-26
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