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EP0362365A1 - Carboxylates surbases borates et non borates a titre d'inhibiteurs de corrosion. - Google Patents

Carboxylates surbases borates et non borates a titre d'inhibiteurs de corrosion.

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Publication number
EP0362365A1
EP0362365A1 EP89904972A EP89904972A EP0362365A1 EP 0362365 A1 EP0362365 A1 EP 0362365A1 EP 89904972 A EP89904972 A EP 89904972A EP 89904972 A EP89904972 A EP 89904972A EP 0362365 A1 EP0362365 A1 EP 0362365A1
Authority
EP
European Patent Office
Prior art keywords
gear oil
weight
borated
overbased carboxylate
overbased
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.)
Granted
Application number
EP89904972A
Other languages
German (de)
English (en)
Other versions
EP0362365B1 (fr
Inventor
Craig Daniel Tipton
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.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP0362365A1 publication Critical patent/EP0362365A1/fr
Application granted granted Critical
Publication of EP0362365B1 publication Critical patent/EP0362365B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • 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
    • C10M135/02—Sulfurised compounds
    • C10M135/04—Hydrocarbons
    • 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
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/18—Tall oil acids
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; 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
    • 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
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10M2223/043—Ammonium or amine salts 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
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    • 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
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2040/02—Bearings

Definitions

  • This invention relates generally to the field of additives which are included within lubricant compositions in order to improve performance characteristics of the lubricants. More specifically, the invention relates to additive compounds which act as corrosion inhibitors within gear oil compositions, the corrosion inhibitors being in the form of borated and non-borated forms of overbased carboxylates.
  • the ability to inhibit corrosion, rust formation, oxidation and deterioration is a very significant property of lubricating compositions and functional fluids.
  • the significance of such properties becomes increasingly important when the lubricant or functional fluid is used in connection with very expensive equipment under severe operating conditions.
  • the significance of the ability to inhibit corrosion is further emphasized when the lubricant, such as a gear oil, is used in an environment such that it comes into contact with water under extreme temperature and pressure conditions. In the absence of a corrosion inhibitor with high performance characteristics the useful life of the machinery will be substantially reduced. Accordingly, many manufacturers of equipment requiring the use of functional fluids and lubricants require that such fluids and lubricants contain corrosion inhibitors.
  • U.S. Patent 3,929,650 to King et al discloses a particulate dispersion of an alkali metal borate.
  • the borate i ⁇ prepared by contacting boric acid with an alkali metal carbonate overbased metal sulfonate within an oleophilic liquid reaction medium.
  • the reactants are contacted at a temperature in the range of 20-200°C for a period of 0.5-7 hours with the molar ratio of the boric acid to the alkaline metal carbonate being in the range of from 1-3.
  • U.S. Patent 3,595,790 to Norman et al discloses a number of different oil soluble highly basic metal salts of various organic acids. Salts of sulfonic acids, carboxylic acids and phosphorus acids are obtained by reacting such acids with an excess amount of a metal base in the presence of an acidic gas such as carbon dioxide and a promoter such a ⁇ alcohol under substantially anhydrous conditions.
  • the basic metal salts are indicated as being useful as additives in crankcase oils (oils of low viscosity compared to gear oils) in order to neutralize undesirable acid bodies formed in crankcase oils during engine operation.
  • the present invention is a corrosion inhibitor additive compound which is used in connection with lubricants in the form of gear oils.
  • the corrosion inhibitor additive is in the form of an overbased carboxylate which is preferably borated.
  • the borated versions of the overbased carboxylate additive of the invention are most generally prepared by reacting a boron reactant (preferably boric acid) with an overbased carboxylate.
  • the invention also relates to a method of improving the corrosion inhibiting properties of a gear oil comprising adding borated and/or non-borated versions of the corrosion inhibitor of the invention to the gear oil which contains small amounts (0.1% to 5% based on the weight of the gear oil) of contaminant water, and allowing the corrosion inhibitor to disperse in the system and thereby improve overall corrosion inhibiting properties.
  • An object of the present invention is to provide a corrosion inhibitor useful in a wide range of lubricating and functional fluid compositions and particularly in gear oils.
  • An advantage of the present invention is that the overbased carboxylate composition of the invention can be easily and economically manufactured and included within lubricating compositions in the form of gear oils to inhibit corrosion, rust formation, oxidation and deterioration.
  • a feature of the present invention is that the corrosion inhibitor additive can be provided in a variety of overbased carboxylate forms. More specifically, the carboxylate acid anion portion as well as the metal cation portion of the molecule are readily available and economical as is the optional borating agent.
  • Another advantage of the corrosion inhibitor composition is that it can provide corrosion resistance properties to a gear oil while not acting in a manner which is antagonistic with respect to high speed score and shock loading protection which antagonistic properties are generally obtained by the use of free carboxylic acids, another well known class of corrosion inhibitors.
  • Yet another advantage of the present invention is that the corrosion inhibitors provide improved properties to gear oils without having a undesirable effect on the oxidation and/or thermal stability of the gear oils, which undesirable effects are obtained when utilizing amine compounds as corrosion inhibitors.
  • the present invention provides a corrosion inhibitor additive which can be used in connection with lubricants and functional fluids.
  • the additive is in the form of an overbased carboxylate which can be in a borated or non- borated form. It is pointed out that the borated versions are generally preferred, and are prepared by reacting a boron reactant (preferably boric acid) with a an overbased carboxylate.
  • a boron reactant preferably boric acid
  • Overbased carboxylates are known to be used in crankcase engine oils (oils of low viscosity compared to gear oils) in order to neutralize acidic components formed during engine operation. These acidic components are formed by "engine blow back" a phenomenon which does not occur in a rear axle assembly.
  • overbased or “overbased compound” or “overbased carboxylate” is generally used to designate metal salts wherein the metal ion is present in stoichiometrically larger amounts than the organic acid radical.
  • the commonly employed methods for preparing overbased compounds involve heating a mineral oil solution of an acid (such as a carboxylic acid) with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50°C and filtering the resulting mass.
  • an acid such as a carboxylic acid
  • a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide
  • a particularly effective method of preparing an overbased carboxylate comprises mixing a carboxylic acid with a stoichiometric excess of a basic alkaline earth neutralizing agent such as calcium hydroxide and at least one alcohol promoter and carbonating the mixture by passing CO- into the mixture at an elevated temperature which may be in the range of 10°C to 200°C but is more preferably in the range of about 40° to 80°C.
  • the present inventor has found that the corrosion inhibiting properties of various lubricating compositions and functional fluids, specifically gear oil formulations, can be greatly improved by including an additive in the form of an overbased carboxylate which is preferably borated.
  • an overbased carboxylate is prepared by reacting a stoichiometric excess of a metal neutralizing agent with a statistical mixture of carboxylic acids to form a statistical mixture of carboxylates which includes a stoichiometric excess of the metal.
  • the anion portion of the present corrosion inhibitor is an ionized carboxylic acid or ionieed carboxylate and is most preferably a statistical mixture of such.
  • a statistical mixture of components is a mixture consisting of a large number of compounds which differ, one from the other, in small increments (e.g. molecular weight and shape) over a wide range.
  • the cationic portion of the present corrosion inhibitor is typically an ion of an alkali metal or an ion of an alkaline earth metal.
  • Some specific metals which might be utilized include lithium, potassium, sodium, magnesium, calcium and barium with sodium, calcium and magnesium being preferred.
  • carboxylic acids may be used individually or preferably in statistical mixtures in producing the present invention.
  • Useful carboxylic acids include oleic acids, tall oil acids, pumitic acids. linoleic acids, stearic acids and lauric acids.
  • Other carboxylic acids which are oil soluble or dispersible in a salt form combination with other additives within lubricants of functional fluids can also be used in connection with the present invention.
  • Useful carboxylic acids generally contain 12 to 22 carbon atoms.
  • the carboxylic acid component is converted to a salt by reacting it with a metal neutralizing agent.
  • the neutralizing agent may be a metal by itself of a metal oxide, hydroxide, carbonate, bicarbonate or sulfide. Such neutralizing agents may be used individually or preferably in combination with each other in a statistical mixture.
  • Sodium, calcium and magnesium metals and metal compounds are preferably used in connection with the present invention.
  • other alkali and alkaline earth metals and compounds thereof may be used in connection with producing the overbased carboxylates of the invention.
  • the overbased carboxylates of the present invention can be obtained by reacting one or more of the carboxylic acids or statistical mixtures thereof indicated above with one or more of the neutralizing agents indicated above.
  • the neutralizing agents are to be added in stoichio ⁇ metrically larger amounts than the organic acid.
  • Means of carrying out the reaction between the organic acid and the neutralizing agent have been indicated above.
  • a typical reaction might involve the reaction of calcium hydroxide and oleic acid in order to form a calcium carboxylate, more specifically, calcium oleate.
  • Such a reaction product could be referred to by the following general empirical formula (I) :
  • R is a hydrocarbyl and X and Y combined are greater than one and vary depending on the degree of overbasing desire. A range of different “R " are present in a preferred statistical mixture of the invention.
  • hydrocarbyl means "hydrocarbon-based.”
  • hydrocarbon-based hydrocarbon-based substi- tuent
  • hydrocarbyl denotes a substituent having a carbon directly attached to the remainder of the molecule and having predominantly hydrocarbyl character within the context of this invention.
  • hydrocarbon substituents that is, aliphatic
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • substituted hydrocarbon substituents that is, those substituents containing nonhydrocarbon radicals which, in the context of this invention, do not alter the predominantly hydrocarbon substituent; those skilled in the art will be aware of such radicals (e.g. , halo (especially chloro and fluoro) , alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.);
  • hereto substituents that is, substituents which will, while having predominantly hydrocarbyl character within the context of this invention, contain other than carbon present in a ring or chain otherwise composed of carbon atoms.
  • Suitable heteroatoms will be apparent to those of ordinary skill in the art and include, for example, sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl, furanyl, thiophenyl, imidazolyl, etc., are exemplary of these hereto substituents heteroatoms and preferably no more than one, will be present for each ten carbon atoms in the hydrocarbon-based substituents.
  • Some preferred carboxylic acids which are used in preparing the overbased carboxylate include tall oil fatty acid, oleic, linoleic acid, and pumitic acids.
  • Some preferred neutralizing agents include sodium hydroxide, calcium hydroxide and magnesium hydroxide.
  • Statistical mixtures of overbased calcium carboxylates are believed to be particularly preferred.
  • the overbased carboxylate may be borated by reacting the carboxylate with a boron reactant.
  • the boron reactant is preferably in the form of boric acid.
  • boric acid i ⁇ charged into the reaction medium containing the overbased carboxylate in an amount necessary in order to form the desired type of borate. Different amounts of H 3 BO- may be charged into the system to obtain the desired amount of borate incorporation depending upon the desired end results and the particular functional fluid or lubricating compositions that the rust inhibitor is to be used in connection with.
  • Useful boron reactants include, boric acid, and various alkylborates such as tri-butylborate and sodium etaborate with boric acid being preferred.
  • the overbased carboxylate can be completely or partially borated with one or more boron reactants.
  • the overbased carboxylate rust inhibitor in its borated and non borated versions may be present in a lubricating composition or functional fluid such as a gear oil in an amount sufficient to improve the rust inhibiting performance characteristics of the lubricant or fluid.
  • This amount can be determined by those skilled in the art and varies depending on factors such as the type of oil base, the end use, and other additives present in the formulation.
  • the rust inhibitor is present in an amount in the range of from about 0.1% to 3%, preferably from about 0.2% ' to about 1.5% and most preferably about 0.5% by weight based on the weight of a fully formulated lubricant or functional fluid.
  • the carboxylic acids from which suitable overbased salts for use in this invention can be made include aliphatic, cycloaliphatic, and aromatic mono- and polybasic carboxylic acids such a ⁇ the napthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, alkyl- or alkenyl-substituted aromatic carboxylic acids.
  • the aliphatic acids generally contain at least 8 carbon atoms and preferably at least 12 carbon atoms. Usually they have no more than about 400 carbon atoms.
  • the acids are more oil-soluble for any given carbon atoms content.
  • the cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, a-linolenic acid, propylene- tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclopentane carboxylic acid, myristic acid, dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, palmitic acid, commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids, and the like. It
  • a typical group of oil-soluble carboxylic acids useful in preparing the salts used in the present inven- tion are the oil-soluble aromatic carboxylic acids. These acids are represented by the general formula:
  • R* is an aliphatic hydrocarbon-based group of at least 4 carbon atoms, and no more than about 400 aliphatic carbon atoms
  • a is an integer from one to four
  • Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms
  • each X* is independently a sulfur or oxygen atom
  • m is an integer of from one to four with the proviso that R* and a are such that there is an average of at least 8 aliphatic carbon atoms provided by the R* groups for each acid molecule represented by Formula IV.
  • aromatic nuclei represented by the variable Ar* are the polyvalent aromatic radicals derived from benzene, napthalene anthracene, phenanthrene, indene, fluorene, biphenyl, and the like.
  • the radical represented by Ar* will be a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthylene, e.g., methyphenylenes, ethoxyphenylenes, nitrophenylenes, isopropylenes, hydroxyphenylenes, mercaptophenylenes, N,N-diethylaminophenylenes, chloro- phenylenes, N,N-diethylaminophenylene ⁇ , chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, and similar tri-, tetra-, pentavalent nuclei thereof, etc.
  • the R* groups are usually hydrocarbyl groups, prefer ⁇ ably groups such as alkyl or alkenyl radicals.
  • the hydrocarbon character is retained for purposes of this invention so long as any non-carbon atoms present in the R* groups do not account for more than about 10% of the total weight of the R* groups.
  • R* groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 4-hexenyl, 3-cyclohexyl- octyl, 4- (p-chlorophenyl) -octyl, 2, 3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and substituents derived from polymerized ole in ⁇ such as polychloroprenes, polyethyl- enes, polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, and the like.
  • the group Ar* may contain non-hydrocarbon substituents, for example, such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less than 4 carbon atoms, hydroxy, mercapto, and the like.
  • carboxylic acids corresponding to Formulae IV-V above are well known or can be prepared according to procedures known in the art.
  • Carboxylic acids of the type illustrated by the above formulae and processes for preparing their overbased metal salts are well known and disclosed, for example, in such U.S. Pat. Nos. as 2,197,832? 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798 and 3,595,791 which are incorporated by refer ⁇ ence herein for their disclosures of acids and methods of preparing overbased salts.
  • a reaction flask Charge a reaction flask with about 506 parts by weight of a mineral oil solution containing about 0.5 equivalent of a substantially neutral magnesium salt of an alkylated salicylic acid wherein the alkyl groups have an average of about 16 to 24 aliphatic carbon atoms together with about 22 parts by weight (about 1.0 equivalent) of a magnesium oxide and about 250 parts by weight of xylene.
  • Heat to a temperature of about 60°C to 70°C. Increase the temperature to about 85°C and add approximately 60 parts by weight of water to the reaction mass and heat to the reflux temperature. Maintain the reaction mass at the reflux temperature of about 95°-100°C for about 1-1/2 hours and subsequently strip at about 155°C, under 40 torr and filter.
  • the filtrate comprise the basic carboxylic magnesium salts containing 274% of the stoichiometrically equivalent amount of magnesium.
  • the filtrate will comprise the basic carboxylic magnesium salts and have a sulfated ash content of 15.7% (sulfated ash) corresponding to 276% of the stoichiometrically equivalent amount.
  • a gear oil formulation by starting with a base oil formulation utilized in making gear oils, specifically SAE 80W-90 (80% 600N + 20% 150 Bright Stock). Add to the base oil composition 0.25% by weight of a borated overbased carboxylate obtained by reacting the overbased carboxylate of Example A with boric acid. Thereafter add a suitable pour point depressant, specifically the reaction product of a maleic anhydride/styrene copolymer with alcohol and an amine, the pour point depressant being added in an amount of 1 weight percent. Add 1% of an amine-neutralized phosphate ester and 0.075 weight percent of an oleamide/linoleamide mixture of hydroxyalkyl dialkyl-phosphorodithioate. Add 0.075 weight percent of polymeric anti-foaming agent and add 3.6% of a sulfurized olefin. Then add 0.08 weight percent of an ashless inhibitor commercially sold as Amoco 158.
  • Formulate a gear oil by starting with a base oil formulation utilized in making gear oils, specifically Exxon Base SAE 80W-90. Add to the base oil composition 0.25% by weight of an overbased carboxylate obtained by the procedure of Example A. Thereafter add 1% by weight of a pour point depressant (a maleic anhydride/styrene copolymer) . Add 1% of an amine-neutralized phosphate ester and 0.75 weight percent of an oleamide/linoleamide mixture of hydroxyalkyl dialkylphosphorodithioate . Add 0.075 weight percent of a polymeric anti-foaming agent and add 3.6% of an sulfurized olefin as an antioxidant.
  • a base oil formulation utilized in making gear oils specifically Exxon Base SAE 80W-90.
  • Add to the base oil composition 0.25% by weight of an overbased carboxylate obtained by the procedure of Example A. Thereafter add 1% by weight of a pour point depressant (a maleic anhydride
  • a gear oil formulation can be prepared by adding to a base oil of Exxon Base SAE 80W-90 3.0% by weight of a borated overbased carboxylate obtained by reacting the overbased carboxylate of Example C with boric acid. Thereafter add 1.0% by weight of a suitable pour point depressant and 1% of an amine-neutralized phosphate ester. Add 0.1% weight percent of a polymeric anti-foaming agent and add 2.0% of. an sulfurized olefin. Then add 3.0 weight percent of an epoxide treated dialkylphosphorodithioate.
  • a gear oil formulation was prepared starting with SEA 80W-90 base oil which was comprised of 75% by weight of 600 neutral oil and 25% of 150 bright stock.
  • To the base oil was added 1% by weight of pour point depressant in the form of a a reaction product obtained by reacting a maleic anhydride/styrene copolymer with ethanol ar.c an amine.
  • An anti-wear agent (3% by weight) was added in the form of an epoxide treated dialkylphsophorodithioate.
  • a gear oil formulation was prepared starting with SEA 80W-90 base oil which was comprised of 75% by weight of 600 neutral oil and 25% of 150 bright stock.
  • SEA 80W-90 base oil which was comprised of 75% by weight of 600 neutral oil and 25% of 150 bright stock.
  • To the base oil was added 1% by weight of a reaction product obtained by reacting a maleic anhydride/styrene copolymer with ethanol and an amine as a viscosity index improver.
  • An anti-wear agent (3% by weight) was added in the form of an epoxide treated dialkylphsophorodithioate.
  • One weight % of calcium carboxylate was added, 0.1 weight % of R-NC 3 H,N (R is tallow) and 0.075 weight % of a polymeric antifoa agent were added to complete the gear oil formulation having improved anti-corrosion properties.
  • a gear oil formulation was prepared starting with SEA 80W-90 base oil which was comprised of 75% by weight of 600 neutral oil and 25% of 150 bright stock.
  • SEA 80W-90 base oil which was comprised of 75% by weight of 600 neutral oil and 25% of 150 bright stock.
  • To the base oil was added 1% by weight of a reaction product obtained by reacting a maleic anhydride/styrene copolymer with ethanol and an amine as a viscosity index improver.
  • a sulfurized olefin was added in an amount of 3% by weight.
  • An anti-wear agent (3% by weight) was added in the form of an epoxide treated dialkylphsophorodithioate.
  • This example was prepared in the same manner as Example 7 except that the 1 weight % of borated calcium carboxylate was not added to the formulation.
  • Example 7 Another comparative formulation was prepared in the same manner as Example 7 except that 1 weight % of an acidic rust inhibitor was added to the formulation in place of the borated calcium carboxylate of Example 7.
  • Example 7 Another comparative formulation was prepared utilizing the same components put forth within Example 7 except that 1 weight % of an extra basic rust inhibitor was added to the formulation ' in place of the borated calcium carboxylate of Example 7.
  • SAE 80W-90 oil As the base oil.
  • SAE 80W-90 oil is preferred but 75W to about 140W oils may be used and may be used in combination with 150 bright stock oil.
  • Base oils used in preparing gear oils are 200 neutral or above, preferably 300N or above and more preferably about 500N to 700N.
  • the viscosity of a gear oil base oil is 40 cSt @ 40°C or higher (6 cSt @ 100°C or higher) preferably 60 cSt @ 40°C or higher (8 cSt @ 100°C or higher) . These readings are well above those of base oils used as lubricants in a crankcase e.g., 5 W and 10W base oil of about 100N and about 20 cSt @ 40°C (4 cSt @ 100°C) .
  • the gear oil formulations of the present invention typically include a suitable pour point depressant compound.
  • the pour point depressant compound is generally present in an amount in the range of about 0.05% to 4%, more preferably 0.5% to 2% by weight based on the weight of the gear oil.
  • a number of useful pour point depressant compositions are known and are used in oils and fuels in order to allow such to flow freely at lower temperatures.
  • Such compounds may typically be comprised of the condensation product of a chlorinated paraffin and an aromatic hydrocarbon such as naphthalene.
  • Gear oil formulations of the present invention also typically include sulfurized olefin compounds which are useful as anti-oxidants. Such compounds are typically prepared by reacting unsaturated olefin compounds with sulfurizing agents such a ⁇ hydrogen sulfide or elemental sulfur under particular reaction conditions and possibly in the presence of a catalyst. A number of sulfurized olefin compositions are disclosed within PCT Publication US86/00884, published December 25, 1986 (incorporated herein by reference to disclose sulfurized olefin compounds) .
  • the gear oil formulations of the present invention may also include therein extreme pressure - anti-wear agents.
  • Such compounds may be in the form of coupled phosphorus containing amides. Such compounds are disclosed within issued U.S. Patent 4,670,169 (incorporated herein by reference for disclosing phosphoru ⁇ containing extreme pressure agents and methods for making such) .
  • Gear oil formulations of the invention may also include other additives in minor amounts such as anti-foam agents which are used to reduce or prevent the formation of stable foam.
  • Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976) , pages 125-162.
  • phosphorodithioate compounds such as group II metal phosphorodithioates such as zinc dicyclohexyl phosphorodithioate and other similar compounds as disclosed within U.S. Patent 4,670,169 (incorporated herein by reference for disclosing such phosphordithioate compounds) .
  • gear oil formulation in addition to the components referred to above it is possible to include within the gear oil formulation other additive components such as dispersants, detergents, anti-oxidants, anti-wear agents, extreme pressure agents, emulsifiers, demulsifiers, friction modifiers, other anti-rust agents and corrosion inhibitors, viscosity improvers, dyes and solvents to improve handleability.
  • additive components such as dispersants, detergents, anti-oxidants, anti-wear agents, extreme pressure agents, emulsifiers, demulsifiers, friction modifiers, other anti-rust agents and corrosion inhibitors, viscosity improvers, dyes and solvents to improve handleability.
  • the L-33 Moisture Corrosion Test will be described first. Moisture which accumulates in a differential assembly of a vehicle can create a severe rust problem.
  • a Dana Model 30 hypoid rear axle assembly is used in a test specifically designed to evaluate corrosion resistance characteristics of gear lubricants.
  • the lubricant capacity i ⁇ 1.2L (2 h pints) .
  • test 29.6 cm (one ounce) of distilled water is added to the lubricant to increase the severity of the test.
  • the unit is motored at 2500 rp for four hours at 82°C
  • the assembly is stored for seven days at a temperature of 52°C (125°F) .
  • the unit is disassembled and the cover plate, differential case, gear teeth and bearings are inspected for rust.
  • no rust is allowed on the gear teeth, bearings or any other functioning part of the rear axle assembly.
  • the cover of the rear axle assembly is more susceptible to rust, and therefore may have no more than 1% of the surface rusted in order to receive a "pass" rating in accordance with the L-33 Moisture Corrosion Test.
  • the L-33 Moisture Corrosion Test is part of the MIL-L-2105C specification for gear lubricants, and is recognized worldwide as a standard for rust performance.
  • the ASTM D 665 Test consists of two parts. One part of the test uses distilled water and the other part uses a synthetic sea water. Both test ⁇ are run under identical conditions and compared. The tests consist of stirring a mixture of 300 ml of the test lubricant with 30 ml of water at 60° (140°F) for 24 hours. A special cylindrical steel test specimen made from #1018 cold finished carbon steel is completely immersed in the test fluid. At the conclusion of the 24 hour period, the specimen is removed, washed with a solvent and rated for rust.

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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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

On a mis au point un additif anti-corrosion pour formulations d'huile pour engrenages, se présentant sous la forme d'un carboxylate surbasé pouvant être sous une forme boratée ou non boratée. On préfére les versions boratées du carboxylate surbasé, que l'on obtient par réaction d'un réactant du bore tel que l'acide borique avec un carboxylate surbasé. On a découvert que le carboxylate surbasé dans ses formes boratée et non boratée, améliore efficacement les propriétés anti-corrosion de formulations d'huile à engrenage que l'on utilise dans des conditions de travail très dures dans lesquelles l'huile pour engrenages pourrait venir au contact d'eau contaminante. On a également mis au point un procédé améliorant la résistance à la corrosion d'une huile pour engrenages dans laquelle se trouve de l'eau contaminante.
EP89904972A 1988-04-08 1989-03-31 Carboxylates surbases borates a titre d'inhibiteurs de corrosion Expired - Lifetime EP0362365B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17908788A 1988-04-08 1988-04-08
US179087 1988-04-08
PCT/US1989/001339 WO1989009811A1 (fr) 1988-04-08 1989-03-31 Carboxylates surbases borates et non borates a titre d'inhibiteurs de corrosion

Publications (2)

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EP0362365A1 true EP0362365A1 (fr) 1990-04-11
EP0362365B1 EP0362365B1 (fr) 1997-10-29

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JP (1) JP2936071B2 (fr)
AT (1) ATE159753T1 (fr)
AU (1) AU626859B2 (fr)
CA (1) CA1317278C (fr)
DE (1) DE68928409T2 (fr)
MX (1) MX170087B (fr)
SG (1) SG47665A1 (fr)
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ZA (1) ZA892471B (fr)

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BR9007186A (pt) * 1990-01-05 1992-01-28 Lubrizol Corp Composicao lubrificante e metodo de lubrificacao de transmissoes e conjuntos de engrenagens
JPH06502683A (ja) * 1991-08-09 1994-03-24 ザ ルブリゾル コーポレイション トリグリセリド、清浄−防止添加剤、および粘度改良添加剤を有する機能性流体
US7163912B2 (en) * 2001-05-18 2007-01-16 Omg Americas, Inc. Lubricant compositions containing an overbased amorphous alkaline earth metal salt as a metal protectant
JP2003138285A (ja) * 2001-11-02 2003-05-14 Nippon Oil Corp 自動車用変速機油組成物

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JPS57200496A (en) * 1981-05-26 1982-12-08 Lubrizol Corp Manufacture of boron-containing composition and boron-containing composition, additive condensate and lubricant composition
EP0119792A3 (fr) * 1983-03-09 1986-07-16 Uniroyal, Inc. Composition lubrifiante de polyisoprène hydrogéné
US4528108A (en) * 1983-04-20 1985-07-09 The Lubrizol Corporation Method for cooling internal combustion engine with an oleaginous coolant fluid composition
US4659488A (en) * 1985-09-18 1987-04-21 The Lubrizol Corporation Metal working using lubricants containing basic alkaline earth metal salts
CA1290741C (fr) * 1986-04-11 1991-10-15 James N. Vinci Compositions de graisse et de lubrifiant pour engrenages, lesdites compositions renfermant au moins une composante a teneur de metal et au moins un compose organique soufre
JP2670669B2 (ja) * 1986-09-01 1997-10-29 昭和シェル石油 株式会社 自動車用ギヤ油組成物
WO1988005810A1 (fr) * 1987-01-30 1988-08-11 The Lubrizol Corporation Composition lubrifiante pour engrenages
DE3885853T2 (de) * 1987-05-07 1994-03-17 Lubrizol Corp Addtivgemisch und damit legiertes getriebeschmiermittel.
AU1727088A (en) * 1987-05-13 1988-12-06 Lubrizol Corporation, The Gear lubricant compositions

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Title
See references of WO8909811A1 *

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WO1989009811A1 (fr) 1989-10-19
JP2936071B2 (ja) 1999-08-23
MX170087B (es) 1993-08-06
ATE159753T1 (de) 1997-11-15
DE68928409D1 (de) 1997-12-04
AU626859B2 (en) 1992-08-13
SG47665A1 (en) 1998-04-17
DE68928409T2 (de) 1998-04-23
CA1317278C (fr) 1993-05-04
AU3446989A (en) 1989-11-03
EP0362365B1 (fr) 1997-10-29
JPH02503929A (ja) 1990-11-15
ZA892471B (en) 1989-12-27

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