EP0313628B1 - Composition additive et lubrifiant pour engrenages combine avec celle-ci - Google Patents

Composition additive et lubrifiant pour engrenages combine avec celle-ci Download PDF

Info

Publication number
EP0313628B1
EP0313628B1 EP88904352A EP88904352A EP0313628B1 EP 0313628 B1 EP0313628 B1 EP 0313628B1 EP 88904352 A EP88904352 A EP 88904352A EP 88904352 A EP88904352 A EP 88904352A EP 0313628 B1 EP0313628 B1 EP 0313628B1
Authority
EP
European Patent Office
Prior art keywords
additive
weight
oil
carboxylate
gear
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88904352A
Other languages
German (de)
English (en)
Other versions
EP0313628A1 (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
Priority to AT88904352T priority Critical patent/ATE97690T1/de
Publication of EP0313628A1 publication Critical patent/EP0313628A1/fr
Application granted granted Critical
Publication of EP0313628B1 publication Critical patent/EP0313628B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary 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
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • 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
    • C10M2207/10—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
    • 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
    • C10M2207/129—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
    • C10M2207/26—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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • 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
    • C10M2215/26—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
    • 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
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • 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
    • C10N2010/02—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to the field of gear lubricants containing additives which improve the performance of the lubricants. More specifically, the invention relates to additives and gear lubricants having therein a combination of components which provide an interdependent synergistic effect on improving numerous characteristics of the gear lubricant.
  • An additive comprising a combination of additive components is often referred to as an "additive package" in the art.
  • Gear lubricant additive packages are included in gear lubricants in order to improve performance characteristics of the lubricant.
  • a number of different additive compounds are known to effect the performance characteristics of a variety of different types of lubricants.
  • a given additive compound can have different effects on performance characteristics depending on the type of lubricant it is added to and the other additive compounds present in the lubricant. Therefore, a formulator must consider not only the principle effects of including a given compound but how the effects of the compound are changed due to the presence of other compounds and the total environment the final product will be used in.
  • U.S. Patent US-A-3,923,669 discloses antiwear hydraulic oils which include therein zinc dialkyl dithiophosphate antiwear agents.
  • the additive package includes neutral barium salts of a petroleum sulfonate and a succinic acid based rust inhibitor.
  • U.S. Patent US-A-3,480,548 discloses lubricating compositions comprised of a major amount of lubricating oil and an additive package which includes an oil soluble normal alkaline earth metal hydrocarbon sulfonate and an alkaline earth metal polyborate alkaline earth metal carbonate in a colloidal-like dispersion.
  • U.S. Patent US-A-3,929,650 discloses a particulate dispersion of an alkali metal borate which is prepared by contacting boric acid with an alkaline earth metal carbonate overbased metal sulfonate within an oleophilic liquid reaction medium. The resulting particulate dispersion is included within a lubricant in order to improve the performance characteristics.
  • U.S. Patent US-A-3,903,003 discloses lubricating oil compositions which are intended for use in connection with internal combustion engines.
  • the lubricating oils include additive packages which comprise an amido amine reaction product formed between certain carboxylated hydrogenated polyisoprenes and certain amines, imines and hydroxyl alkyl polyamines.
  • the additive is indicated as being used in connection with a number of different types of lubricants including gear lubricants.
  • U.S. Patent US-A-4,563,302 discloses sulfurized olefins which are utilized in connection with lubricating oils in order to improve the stability of the oil. A specific process for manufacturing such sulfurized olefins is disclosed.
  • U.S. Patent US-A-4,481,122 discloses lubricating compositions which include major amounts of a base oil and a minor amount of an additive which comprises an oil soluble polymer such as polyisobutylene. Specific compounds such as an organo silicone anti foaming agent is also indicated as being included within the lubricating oil.
  • GB-A-1,121,713 relates to lubricant compositions comprising (A) an alkaline earth metal salt of an acidic, phosphosulfurized olefin polymer having a molecular weight of at least 10,000; (B) a fatty acid derivative having at least 12 aliphatic carbon atoms selected from the class consisting of alkaline earth metal salts, aliphatic esters, and sulfurized aliphatic esters; (C) a compound selected from the class consisting of Group II metal phosphorothioate adducts of Group II metal phosphorothioates with an alkylene oxide; di- and tri-esters of phosphorous acid; phosphosulfurized terpene; and substantially hydrocarbon sulfides or polysulfides; and (D) a polar substituted amine which is prepared by reacting an alkylene polyamine with a substantially hydrocarbon substituted succinic acid producing compound.
  • Component B, Additive 1 is a barium
  • U.S. Patent US-A-3,190,833 relates to oxidation-resistant lubricating compositions and discloses a Group II metal phosphorodithioate treated with an epoxide.
  • optional additives which include inter alia (a) neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids or organic phosphorous acids, and (b) sulfurized dipentene and sulfurized terpene (dipentene is in fact a terpene).
  • One method of preparing the basic salts involves using a promoter which may, inter alia, be dodecylamine.
  • U.S. Patent US-A-3,813,336 relates to anti-wear and antioxidant lubricant additives prepared by the reaction products of amines with dithiophosphoric acids and salts.
  • the invention provides the use of an additive, comprising:
  • Desirable properties which can be achieved using the invention include:-
  • the additive used in the invention must include (a) a treated zinc dithiophosphate and (b) an overbased carboxylate.
  • the combination of (a) and (b) is useful as an additive package for its ability to improve the corrosion resistance and anti-wear properties of a gear lubricant oil.
  • the components of the additive combination provide an interdependent synergistic improvement of numerous performance characteristics such as preventing copper strip corrosion, increasing thermal stability, reducing the amount of rust and odor, and improving limited slip or anti-chatter performance.
  • Each of the specific components of the additive combination will now be described in detail in order to describe and disclose a representative number of examples of such components which might be used in connection with the present invention.
  • Zinc dithiophosphate compounds are useful additives as anti-wear agents in various types of lubricants.
  • Zinc dithiophosphates continue to provide one of the most economical sources of anti-wear protection.
  • the zinc in the structure for zinc dithiophosphate (shown below) is derived from a primary alcohol, then the zinc is referred to as primary; likewise, if it is derived from a secondary alcohol, it is referred to as secondary and, if derived from a phenol or an alkylated phenol, it is referred to as aryl.
  • Each of these zincs usually displays a different combination of performance properties as summarized below: Performance Characteristic Type of Zinc Dithiophospate Primary Secondary Aryl Wear Protection Average Best Poorest Oxidation Inhibition Average Best Poorest Thermal Stability Average Poorest Best Demulsibility Best Average Poorest Cost Lowest Average Highest NOTE - Variations are present among different compounds in any given class. Further, different sources may rate any given performance characteristics differently.
  • zincs are selected for a particular application.
  • aryl zincs are used almost exclusively in diesel engine oils because of their excellent thermal stability.
  • Primary zincs find a large application in both engine oils and hydraulic oils.
  • Secondary zincs are used mostly in hydraulic oils, transmission and gear oils.
  • Primary and secondary zincs have been selected for these applications because of their relatively good anti-wear performance, good anti-oxidant qualities and low cost. Where hydraulic oils are concerned, primary zincs have usually been preferred because they offered the best overall performance for the lowest cost.
  • zinc dithiophosphate may be present.
  • the present invention uses zinc dithiophosphate, preferably secondary zinc dithiophosphates as intermediates by reacting the zinc dithiophosphate with a treating agent selected from alkylene oxides containing 2 to 5 carbon atoms, ethylene diamine and combinations thereof.
  • the invention may include untreated zinc dithiophosphate in combination with those treated with one or more of the above mentioned treating agents.
  • Most preferably the invention includes a propylene oxide treated secondary zinc dithiophosphate.
  • the treated zinc dithiophosphate may be present in the gear oil in an amount in the range of from about 0.1% to 5% by weight based on the weight of the oil, more preferably about 2.0% to 4.0% by weight and most preferably about 3.0% by weight.
  • the amount of this component like the other components can be adjusted by those skilled in the art to obtain the best results in a given environment.
  • This component is present in the fully formulated gear oil in an amount sufficient to act as an EP/antiwear agent in the system.
  • the treatment with a compound like propylene oxide decreases the potential corrosivity of this component as used in a system.
  • the overbased carboxylate component (b) of the present invention is in a borated form and is most generally prepared by reacting a boron reactant (preferably boric acid) with an overbased carboxylate.
  • overbased compound is generally used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical.
  • the commonly employed methods for preparing overbased compounds involves heating a mineral oil solution of an 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.
  • a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide
  • promoter in the neutralization step to aid the incorporation of a large excess of metal is generally found to be useful.
  • a particularly effective method of preparing a basic salt comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter and carbonating the mixture by passing CO2 into the mixture at an elevated temperature between 10°C and 200°C.
  • the overbased compound is an overbased carboxylate prepared by reacting a stoichiometric excess of a metal neutralizing agent with a carboxylic acid to form a carboxylate which includes a stoichiometric excess of the metal.
  • the anion portion of the overbased component is an ionized carboxylic acid or carboxylate.
  • the cationic portion of the overbased component is typically an ionized alkali metal or alkaline earth metal.
  • the commonly used alkaline metals are lithium, potassium and sodium, with sodium being preferred.
  • the alkaline earth metal components typically utilized are magnesium, calcium, and barium with calcium and magnesium being preferred.
  • a typical calcium carboxylate can be represented empirically by Ca(RCOO)2 . XCa (OH)2 . YCaCO3 where R is a hydrocarbyl as defined below and X and Y combined are greater than 1 and vary depending on the degree of overbasing desired.
  • Some typical carboxylic acids used in preparing a carboxylate include tall oil fatty acid, oleic acid, linoleic acid, linolenic, and palmitic acids. The use of overbased calcium carboxylate of these acids are preferred.
  • the component is borated by reacting with a boron reactant which is preferably boric acid.
  • a boron reactant which is preferably boric acid.
  • the boric acid is charged into the reaction medium in the desired amount in order to form different types of borates. Different amounts of H3BO3 may be charged into the system to obtain the desired amount of boron incorporation depending on the desired end results.
  • the borated overbased carboxylate component (b) may be present in the gear oil 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 the fully formulated gear oil.
  • the alkylamine component (d) of the present invention may be a mono, di or polyamine. Further, it may be a primary, second or tertiary amine. However, in connection with the present invention it is preferred if the amine is a diamine compound represented by the general formula (I) RNH(CH2)3NH2 wherein R is hydrocarbyl. However, R is preferably an alkyl moiety containing about 10 to about 20 carbon atoms.
  • hydrocarbyl means "hydrocarbon-based”.
  • hydrocarbon-based hydrocarbon-based substituent
  • 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.
  • radicals or heteroatoms In general, no more than about three radicals or heteroatoms and preferably no more than one, will be present for each ten carbon atoms in the hydrocarbon-based substituents. Typically, there will be no such radicals or heteroatoms in the hydrocarbon-based substituent and it will, therefore, by purely hydrocarbon.
  • the alkylamine component (d) may be present in the gear oil in an amount in the range of from about 0.05% to about 1.0% by weight, preferably 0.1% to 0.4% and most preferably about 0.2% by weight based on the weight of the the gear oil as a whole.
  • Patent US-A-3,471,404 describes a product in which sulfur monochloride is reacted with olefin to obtain an intermediate which is reacted with sulfur and alkali metal sulfide at a critical ratio of 1.8-2.2 gram moles of metal sulfide per gram mole of sulfur. This material is then refluxed for 1-24 hours with aqueous alkali metal hydroxide.
  • sulfur monochloride is reacted with olefin to obtain an intermediate which is reacted with sulfur and alkali metal sulfide at a critical ratio of 1.8-2.2 gram moles of metal sulfide per gram mole of sulfur.
  • This material is then refluxed for 1-24 hours with aqueous alkali metal hydroxide.
  • an effective sulfurized olefin is made by reacting a sulfur monochloride with an olefin in the presence of a lower alkanol promoter to obtain an adduct which is reacted with sodium sulfide and sulfur in aqueous alkanol.
  • a sulfurized olefin having improved solubility especially in a-olefin oligomer lubricating oil is made by reacting a monoolefin with S2Cl2 or SCl2 to obtain an adduct which is reacted with sodium sulfide, sulfur, alkyl mercaptan and optionally sodium hydrosulfide in an aqueous alcohol reaction medium.
  • S2Cl2 or SCl2 sulfur, alkyl mercaptan and optionally sodium hydrosulfide in an aqueous alcohol reaction medium.
  • a process for making a sulfurized olefin having improved solubility in lubricating oil comprises:
  • a useful product can be obtained using either SCl2 or S2Cl2.
  • Useful olefins are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefin containing 3 to about 6 carbon atoms. These include 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 2-ethyl-2-butene and the like including mixtures thereof.
  • the olefins are branched-chain olefin such as isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-2-pentene and the like. More preferably the ethylenic double bond adjoins a tertiary carbon atoms such as isobutylene, the most preferred olefin.
  • the sulfurized olefin component (c) may be present in the gear oil in an amount in the range of from about 0.5% to about 8.0% by weight, preferably 3.0% to 4.0% and most preferably about 3.0% by weight based on the weight of the gear oil as a whole.
  • a specific foam inhibitor which is commercially available from Monsanto is referred to as defoamer PC-1244.
  • a specific copolymer defoamer compound is the copolymer of 2-ethylhexylacrylate/ethylacrylate in a weight ratio of 2.5:1.
  • the copolymer is generally present in an amount of 40% by weight of active chemical in a toluene diluent.
  • the copolymer is made by adding a mixture of monomers together with an initiator in toluene solvent in the proper proportions to a "heel.”
  • the reactants are combined together in a polymerization vessel at about 110°C.
  • the resulting product is a polymer having a molecular weight in the range of about 40,000 and 90,000 (Mw). Wherein the Mn is in the range of 16,000-25,000.
  • the viscosity at 40°C is approximately 15cSt.
  • foam inhibitors may be found to be useful in connection with the present invention.
  • polymeric foam inhibitors may be added in an amount of from about 0.01 to 1.0%, preferably 0.03 to 0.1 and most preferably about 0.075% by weight based on the weight of the fully formulated gear oil.
  • An additive concentrate is prepared by combining 3% propylene oxide treated zinc dithiophosphate, 3% sulfurized olefin, 0.2% oleylamine plus 0.5% borated overbased fatty calcium carboxylate and 0.075% commercial polymeric foam inhibitor containing 40% active chemical. The components are added to a diluent oil to provide a 7.0% by weight concentrate.
  • Example 1 The procedure of Example 1 is followed except that the 0.5% borated overbased fatty calcium carboxylate is replaced with 1.0% weight overbased fatty calcium carboxylate (non-borated) to make a 7.5% by weight concentrate.
  • a fully formulated gear oil can be prepared by combining about 92% of a mineral oil or combination of mineral oils such as (75% 600N + 25% by weight 150 bright stock) with 7.0% weight concentrate described in Example 1 above and 1.0% weight polymeric pour point depressant.
  • a fully formulated gear oil is prepared by adding to a mineral oil of lubricating viscosity, such as bright stock, about 0.1% to 5% of propylene oxide treated zinc dithiophosphate, about 0.1% to about 3.0% of borated overbased carboxylate, about 0.05% to about 1.0% of an alkylamine, about 0.5% to about 8.0% of a sulfurized olefin, and about 0.01% to about 1.0% of a polymeric foam inhibitor.
  • a fully formulated gear oil is prepared by adding to a bright stock mineral oil 3.0 parts by weight of a propylene oxide treated zinc dithiophosphate, 0.5 parts by weight of a borated overbased magnesium carboxylate, 0.2 parts by weight of an alkylamine, and 3 parts by weight of a sulfurized olefin.
  • the resulting fully formulated gear oil should contain 6.7 parts by weight of additive components with the remaining 93.3 parts by weight being bright stock mineral oil.
  • a gear lubricant additive package is prepared by combining together about 0.05 to 5.0 parts by weight of a propylene oxide treated zinc dithiophosphate and about 0.1 to about 3.0 parts by weight of a borated overbased carboxylate.
  • the additive components may be added to a small amount of mineral oil to act as a diluent oil.
  • the additive is useful as an additive for combining with oils which contain an alkylamine and a sulfurized olefin.
  • the additive package may be sold by itself or in concentrates, in combination with any other known additive which includes, but is not limited to dispersants, detergents, antioxidants, antiwear agents, extreme pressure agents, emulsifiers, demulsifiers, friction modifiers, anti-rust agents, corrosion inhibitors, viscosity improvers, dyes, and solvents to improve handleability which may include alkyl and/or aryl hydrocarbons.
  • additives may be present in various amounts depending on the needs of the final product.
  • the concentrate might contain 0.01 to 90% by weight of the additive package.
  • the additive package may be present in a final product, blend or concentrate in (in a minor amount i.e., up to 50% by weight) any amount effective to improve the performance of characteristics of a gear oil but it is preferably present in gear oils in the form of mineral oils of lubricating viscosity in an amount of from about 1% to about 10%, preferably about 2% to about 8%, most preferably about 6.775% by weight based on the weight of the fully formulated gear oil; where the individual components are present in amounts as follows: (a) about 3.0% (b) about 0.5% (c) about 0.2% (d) about 3.0% and (e) about 0.075%.
  • the amounts of the additive package and individual components in the gear oil will be varied by those skilled in the art to obtain optimal performance. For example, smaller amounts of additive (1-3%) are generally used with industrial gear oils.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Un certain nombre de caractéristiques fonctionnelles d'un lubrifiant pour engrenages sont améliorées en additionnant au lubrifiant un mélange additif comprenant (a) un dithiophosphate de zinc traité et (b) un carboxylate surbasé qui est de préférence boré. L'additif comprend de préférence (c) une alkylamine, (d) une oléfine sulfurée et (e) un inhibiteur de mousse polymère. Les composants du mélange permettant d'obtenir une amélioration synergique interdépendante de nombreuses caractéristiques du lubrifiant pour engrenages, telles que la réduction de la corrosion de la bande de cuivre, l'accroissement de la stabilité thermique et la réduction de la quantité de rouille et de l'odeur. Est également améliorée la propriété antiglissement et antibroutement de l'huile.

Claims (6)

  1. Utilisation d'un additif comportant :
    (a) un dithiophosphate de zinc traité, dans lequel le dithiophosphate de zinc est traité au moyen d'un oxyde d'alcylène comportant de 2 à 5 atomes de carbone et/ou d'une éthylène diamine ;
    (b) un carboxylate boraté surbasé ;
    (c) une oléfine sulfurée ;
    (d) une alkylamine ; et
    (e) un inhibiteur de mousse, polymèrique ;
    en tant qu'agent anti-corrosion dans un lubrifiant pour engrenages.
  2. Utilisation selon la revendication 1, dans laquelle le carboxylate surbasé (b) est un carboxylate de lithium, de potassium, de sodium, de magnésium ou de calcium, surbasé.
  3. Utilisation selon la revendication 1, dans laquelle le carboxylate surbasé (b) est un carboxylate de calcium.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le dithiophosphate de zinc est traité avec de l'oxyde de propylène.
  5. Utilisation selon la revendication 1, dans laquelle l'alkylamine est représentée par la formule générale (I):
    Figure imgb0004
     dans laquelle R est un hydrocarbyle.
  6. Utilisation selon la revendication 5, dans laquelle R est un groupement alkyle renfermant de 10 à 20 atomes de carbone.
EP88904352A 1987-05-07 1988-04-29 Composition additive et lubrifiant pour engrenages combine avec celle-ci Expired - Lifetime EP0313628B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88904352T ATE97690T1 (de) 1987-05-07 1988-04-29 Addtivgemisch und damit legiertes getriebeschmiermittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4775487A 1987-05-07 1987-05-07
US47754 1993-04-13

Publications (2)

Publication Number Publication Date
EP0313628A1 EP0313628A1 (fr) 1989-05-03
EP0313628B1 true EP0313628B1 (fr) 1993-11-24

Family

ID=21950782

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88904352A Expired - Lifetime EP0313628B1 (fr) 1987-05-07 1988-04-29 Composition additive et lubrifiant pour engrenages combine avec celle-ci

Country Status (7)

Country Link
EP (1) EP0313628B1 (fr)
JP (1) JPH01503392A (fr)
AU (1) AU602773B2 (fr)
CA (1) CA1312070C (fr)
DE (1) DE3885853T2 (fr)
WO (1) WO1988008874A2 (fr)
ZA (1) ZA883229B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU626859B2 (en) * 1988-04-08 1992-08-13 Lubrizol Corporation, The Borated and non-borated overbased carboxylates as corrosion inhibitors
GB2288815A (en) * 1994-04-08 1995-11-01 Exxon Chemical Patents Inc Lubricating oil anti-wear additives
US20090093384A1 (en) * 2007-10-03 2009-04-09 The Lubrizol Corporation Lubricants That Decrease Micropitting for Industrial Gears
CN113637514A (zh) 2013-12-06 2021-11-12 巴斯夫欧洲公司 组合物及其形成方法
WO2018057675A1 (fr) * 2016-09-21 2018-03-29 The Lubrizol Corporation Composants antimousse polyacrylate à stabilité thermique améliorée

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3813336A (en) * 1970-09-11 1974-05-28 Chevron Res Reaction products of amines and dithiophosphoric acids or salts

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3190833A (en) * 1961-04-14 1965-06-22 Lubrizol Corp Oxidation-resistant lubricating composition
GB1121713A (en) * 1966-05-31 1968-07-31 Lubrizol Corp Lubricant additive composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3813336A (en) * 1970-09-11 1974-05-28 Chevron Res Reaction products of amines and dithiophosphoric acids or salts

Also Published As

Publication number Publication date
WO1988008874A2 (fr) 1988-11-17
DE3885853D1 (de) 1994-01-05
AU602773B2 (en) 1990-10-25
ZA883229B (en) 1988-11-11
AU1724488A (en) 1988-12-06
JPH01503392A (ja) 1989-11-16
DE3885853T2 (de) 1994-03-17
WO1988008874A3 (fr) 1988-12-15
EP0313628A1 (fr) 1989-05-03
CA1312070C (fr) 1992-12-29

Similar Documents

Publication Publication Date Title
JP2997057B2 (ja) 動力伝達用組成物中において有用な低圧誘導混成燐―及び硫黄含有反応生成物並びにそれらの製造法
AU702057B2 (en) Lubricant compositions to reduce noise in a push belt continuous variable transmission
EP1907517B1 (fr) Tungstates d'amine et diarylamines dans des compositions de graissage
US4428849A (en) Lubricating oil with improved diesel dispersancy
US4192757A (en) Alkyl phenol solutions of organo molybdenum complexes as friction reducing antiwear additives
CA1238345A (fr) Alcoyl(c in18 xx a c in24 xx)-catechols normalement liquides
EP0041597A2 (fr) Additifs à base d'organomolybdène et compositions lubrifiantes les contenant
JPH04345690A (ja) スクシンイミド組成物
JPH01502988A (ja) リン含有およびイオウ含有の潤滑剤および機能流体組成物
US5152908A (en) Gear lubricant package containing a synergistic combination of components
EP0562062B1 (fr) Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage
US5573696A (en) Oil-soluble phosphorus- and nitrogen-containing additives
US4632771A (en) Normally liquid C14 to C18 monoalkyl catechols
EP0313628B1 (fr) Composition additive et lubrifiant pour engrenages combine avec celle-ci
EP0735129B1 (fr) Additifs solubles dans d'huile, contenant du phosphore et nitrogène
EP0348236B1 (fr) Combinaison synergique d'additifs utile dans les compositions de transmission de puissance
DE4317105A1 (de) Schmiermittel mit verbesserten Eigenschaften bei niedriger Temperatur
US4629577A (en) Method for improving fuel economy of internal combustion engines
EP0556404A1 (fr) Composition d'huile lubrifiante
JP3650635B2 (ja) モリブデン含有摩擦低減用添加剤
JPH01304185A (ja) 潤滑油組成物
US4317739A (en) Aminated sulfurized olefin funtionalized with a boron compound and formaldehyde
EP0353854A1 (fr) Modificateur de friction à base d'hydroxy ether amine pour fluides de transmission et additifs anti-usure utiles en combinaison avec celui-ci
US5028345A (en) Lubricating oil composition
JPH075904B2 (ja) 少なくとも１種の金属含有組成物，および少なくとも１種の硫化された有機化合物を含有する，グリース潤滑組成物およびギア潤滑組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890120

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19891106

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 97690

Country of ref document: AT

Date of ref document: 19931215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3885853

Country of ref document: DE

Date of ref document: 19940105

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

ET Fr: translation filed
EPTA Lu: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 88904352.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19950301

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19950313

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19950314

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19950430

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19960429

Ref country code: AT

Effective date: 19960429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19960430

Ref country code: CH

Effective date: 19960430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19961101

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19961101

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19980319

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

EUG Se: european patent has lapsed

Ref document number: 88904352.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000330

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000421

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010402

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010403

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20010430

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010430

BERE Be: lapsed

Owner name: THE LUBRIZOL CORP.

Effective date: 20010430

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050429