EP1386956B1 - Hydratisiertes Alkalimetallborat und hexagonales Bornitrid enthaltende Additivzusammensetzung für Getriebeöle - Google Patents

Hydratisiertes Alkalimetallborat und hexagonales Bornitrid enthaltende Additivzusammensetzung für Getriebeöle Download PDF

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Publication number
EP1386956B1
EP1386956B1 EP02291928A EP02291928A EP1386956B1 EP 1386956 B1 EP1386956 B1 EP 1386956B1 EP 02291928 A EP02291928 A EP 02291928A EP 02291928 A EP02291928 A EP 02291928A EP 1386956 B1 EP1386956 B1 EP 1386956B1
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Prior art keywords
oil
alkali metal
additive composition
oil dispersion
metal borate
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EP02291928A
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English (en)
French (fr)
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EP1386956A1 (de
Inventor
Pierre Tequi
Sylvain Iovine
Bernard Constans
Raphaèle Ladaviere
Jean Michel Martin
Thierry Le Mogne
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Chevron Oronite SAS
Total Marketing Services SA
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Chevron Oronite SAS
Total Raffinage Marketing SA
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Priority to ES02291928T priority Critical patent/ES2329446T3/es
Priority to AT02291928T priority patent/ATE435268T1/de
Priority to EP02291928A priority patent/EP1386956B1/de
Priority to DE60232788T priority patent/DE60232788D1/de
Priority to US10/624,240 priority patent/US20040147409A1/en
Priority to CA2493288A priority patent/CA2493288C/en
Priority to JP2004525416A priority patent/JP4391937B2/ja
Priority to AU2003260447A priority patent/AU2003260447A1/en
Priority to PCT/EP2003/009312 priority patent/WO2004013262A1/en
Publication of EP1386956A1 publication Critical patent/EP1386956A1/de
Priority to US11/999,712 priority patent/US20080153724A1/en
Application granted granted Critical
Publication of EP1386956B1 publication Critical patent/EP1386956B1/de
Priority to US13/416,392 priority patent/US20120172264A1/en
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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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions

Definitions

  • This invention is directed to an additive composition for a transmission oil. More particularly, this invention is directed to an additive composition comprising an oil dispersion of a hydrated alkali metal borate and an oil dispersion of hexagonal boron nitride, as well as lubricating oil compositions containing the same
  • E.P. extreme-pressure
  • alkali metal borates are well known extreme-pressure agents for such compositions.
  • 1-11,13 E.P. agents are added to lubricants to prevent destructive metal-to-metal contact in the lubrication of moving surfaces. While under normal conditions termed “hydrodynamic", a film of lubricant is maintained between the relatively moving surfaces governed by lubricant parameters, and principally viscosity.
  • E.P. agents have been oil soluble or easily dispersed as a stable dispersion in the oil, and largely have been organic compounds chemically reacted to contain sulfur, halogen (principally chlorine), phosphorous, carboxyl, or carboxylate salt groups which react with the metal surface under boundary lubrication conditions. Stable dispersions of hydrated alkali metal borates have also been found to be effective as E.P. agents.
  • hydrated alkali metal borates are insoluble in lubricant oil! media
  • the degree of formation of a homogenous dispersion can be correlated to the turbidity of the oil after addition of the hydrated alkali metal borate with higher turbidity correlating to less homogenous dispersions.
  • dispersants include lipophilic surface-active agents such as alkenyl succinimides or other nitrogen containing dispersants as well as alkenyl succinates. 1-4,12 It is also conventional to employ the alkali metal borate at particle sizes of less than 1 micron in order to facilitate the formation of the homogenous dispersion. 11
  • anti-sticking agents are often employed in automotive gear boxes to provide smooth synchronization and good shiftability.
  • anti-sticking agents include phosphates, phosphites, phosphionates, thiophosphates, carbamates, molybdenum dithiocarbamates and dithiophosphates.
  • boron nitride exhibits friction modifying properties in lubricants.
  • U.S. Patent No. 4,787,993, issued November 29, 1988 to Nagahiro discloses a lubricant effective for the reduction of friction which comprises dispersing a finely powdered aromatic or polyamide resin into a fluid fat or oil, which may additionally contain molybdenum disulfide, organic molybdenum or boron nitride
  • U.S. Patent No. 4,715,972 issued December 29, 1987 to Pacholke, discloses a solid lubricant additive for gear oils comprising solid lubricant particles combined with a stabilizing agent and a fluid carrier, wherein the solid lubricant particles are selected from the group consisting of molybdenum disulfide, graphite, cerium fluoride, zinc oxide, tungsten disulfide, mica, boron nitrate, boron nitride, borax, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, fluorinated carbon, PTFE, intercalated graphite, zinc phosphide, zinc phosphate, and mixtures thereof.
  • This patent further discloses that such lubricant additive provides the gear oil with improved demulsibility, stability and compatibility characteristics of the gear oil when contaminated with water.
  • the present invention provides a novel additive composition for a transmission oil comprising:
  • the present invention further provides a lubricating oil composition comprising a major amount of a transmission oil of lubricating viscosity and an effective synchronizer sticking reducing amount of the additive composition described above.
  • the transmission oil is a manual transmission gear oil,
  • the present invention is based in part upon the surprising discovery that the unique combination of an oil dispersion of a hydrated alkali metal borate and an oil dispersion of hexagonal boron nitride provides a significant and unexpected reduction in synchronizer sticking when used as an additive composition in a manual transmission gear oil.
  • the present invention is directed to a novel additive composition for a transmission oil comprising (a) an oil dispersion of a hydrated alkali metal borate, and (b) an oil dispersion of hexagonal boron nitride, wherein the. weight ratio of the hydrated alkali metal borate to the hexagonal boron nitride is in the range of 95:5 to 5:95
  • the oil dispersion of hydrated alkali metal borate will contain a hydrated alkali metal borate, a dispersant, optionally a detergent, and an oil of lubricating viscosity.
  • the dispersant employed in the oil dispersion of hydrated alkali metal borate will be selected from the group consisting of a polyalkylene succinimide, a polyalkylene succinic anhydride, a polyalkylene succinic acid, a mono- or di-salt of a polyalkylene succinic acid, and mixtures thereof.
  • the oil dispersion of hydrated alkali metal borate will also contain a detergent, such as a metal sulfonate, preferably an alkylaromatic calcium sulfonate or other Group II metal sulfonate that acts in the present compositions to help provide for a homogeneous dispersion,
  • a detergent such as a metal sulfonate, preferably an alkylaromatic calcium sulfonate or other Group II metal sulfonate that acts in the present compositions to help provide for a homogeneous dispersion
  • the oil dispersion of hydrated alkali metal borate preferably includes those compositions comprising from 10 to 75 weight percent of the hydrated alkali metal borate; from 2 to 40 weight percent of a dispersant, and from 30 to 70 weight percent of an oil of lubricating viscosity, all based on the total weight of the oil dispersion.
  • Hydrated alkali metal borates are well known in the art.
  • Representative patents disclosing suitable borates and methods of manufacture include: U.S. Patent Nos 3,313,727 ; 3,819,521 ; 3,853,772 ; 3,912,643 ; 3,997,454 ; and 4.089,790 . 1-6
  • the hydrated alkali metal borates suitable for use in the present invention can be represented by the following general formula: M 2 O•xB 2 O 3 •yH 2 O wherein M is an alkali metal, preferably sodium or potassium; x is a number from 25 to 4.5 (both whole and fractional); and y is a number from 1.0 to 4.8. More preferred are the hydrated potassium borates, particularly the hydrated potassium triborates.
  • the hydrated borate particles will generally have a mean particle size of less than 1 micron.
  • the ratio of boron to alkali metal will preferably range from 2.5:1 to 4.5:1.
  • Oil dispersions of hydrated alkali metal borates are generally prepared by forming, in deionized water, a solution of alkali metal hydroxide and boric acid, optionally in the presence of a small amount of the corresponding alkali metal carbonate. The solution is then added to a lubricant composition comprising an oil of lubricating viscosity, a dispersant and any optional additives to be included therein (e.g., a detergent, or other optional additives) to form an emulsion that is then dehydrated.
  • a lubricant composition comprising an oil of lubricating viscosity, a dispersant and any optional additives to be included therein (e.g., a detergent, or other optional additives) to form an emulsion that is then dehydrated.
  • these complexes are referred to as “hydrated alkali metal borates” and compositions containing oil/water emulsions of these hydrated alkali metal borates are referred to as "oil dispersions of hydrated alkali metal borates”.
  • Preferred oil dispersions of alkali metal borates will have a boron to alkali metal ratio of 2.5:1 to 4.5:1.
  • the hydrated alkali metal borate particles generally will have a mean particle size of less than 1 micron.
  • the hydrated alkali metal borates employed in this invention preferably will have a particle size where 90% or greater of the particles are less than 0.6 microns.
  • the hydrated alkali metal borate will generally comprise 10 to 75 weight percent, preferably 25 to 50 weight percent, more preferably 30 to 40 weight percent of the total weight of the oil dispersion of the hydrated borate. (Unless otherwise stated, all percentages are in weight percent.)
  • the additive compositions and lubricant compositions of this invention can further employ surfactants, detergents, other dispersants and other conditions as described below and known to those skilled in the art.
  • the additive compositions contain an alkylaromatic or polyisobutenyl sulfonate.
  • the oil dispersions of hydrated alkali metal borates employed in this invention generally comprise a dispersant, an oil of lubricating viscosity, and optionally a detergent, that are further detailed below.
  • the dispersant employed in the oil dispersion of hydrated alkali metal borate used in this invention can be ashless dispersants such as an alkenyl succinimide, an alkenyl succinic anhydride, an alkenyl succinate ester, and the like, or mixtures of such dispersants.
  • Ashless dispersants are broadly divided into several groups.
  • One such group is directed to copolymers which contain a carboxylate ester with one or more additional polar function, including amine, amide, imine, imide, hydroxyl carboxyl, and the like. These products can be prepared by copolymerization of long chain alkyl acrylates or methacrylates with monomers of the above function.
  • Such groups include alkyl methacrylate-vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethy methacrylate copolymers and the like.
  • amides and polyamides or esters and polyesters such as tetraethylene pentamine, polyvinyl polysterarates and other polystearamides may be employed.
  • Preferred dispersants are N-substituted long chain alkenyl succinimides.
  • Alkenyl succinimides are usually derived from the reaction of alkenyl succinic acid or anhydride and alkylene polyamines. These compounds are generally considered to have the formula wherein R 1 is a substantially hydrocarbon radical having a molecular weight from 400 to 3000, that is, R 1 is a hydrocarbyl radical, preferably an alkenyl radical, containing 30 to 200 carbon atoms; Alk is an alkylene radical of 2 to 10, preferably 2 to 6, carbon atoms, R 2 , R 3 , and R 4 are selected from a C 1 -C 4 alkyl or alkoxy or hydrogen, preferably hydrogen, and x is an integer from 0 to 10, preferably 0 to 3.
  • reaction product of alkylene succinic acid or anhydride and alkylene polyamine will comprise the mixture of compounds including succinamic acids and succinimides. However, it is customary to designate this reaction product as a succinimide of the described formula, since this will be a principal component of the mixture. See, for example, U.S. Patent Nos 3,202,678 ; 3,024,237 ; and 3,172,892 .
  • N-substituted alkenyl succinimides can be prepared by reacting maleic anhydride with an olefinic hydrocarbon followed by reacting the resulting alkenyl succinic anhydride with the alkylene polyamine.
  • the R 1 radical of the above formula that is, the alkenyl radical, is preferably derived from a polymer prepared from an olefin monomer containing from 2 to 5 carbon atoms.
  • the alkenyl radical is obtained by polymerizing an olefin containing from 2 to 5 carbon atoms to form a hydrocarbon having a molecular weight ranging from 400 to 3000.
  • Such olefin monomers are exemplified by ethylene, propylene, 1 -butene, 2-butane, isobutene, and mixtures thereof.
  • the preferred polyalkylene amines used to prepare the succinimides are of the formula: wherein z is an integer of from 0 to 10 and Alk, R 2 , R 3 , and R 4 are as defined above.
  • the alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines and also the cyclic and the higher homologs of such amines as piperazine and amino alkyl-substituted piperazines.
  • ethylene diamine triethylene tetraamine, propylene diamine, decamethyl diamine, octamethylene diamine, diheptamethylene triamine,tripropylene tetraamine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, ditrimethylene triamine, 2-heptyl-3-(2-aminopropyl)-imidazoline, 4-methyl imidazoline, N,N-dimethyl-1,3-propane diamine, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)-piperazine, 1 ,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine.
  • Higher homologs such as are obtained by condensing two or more of the above-illustratad alkylene amines likewise are useful.
  • ethylene amines are especially useful. They are described in some detail under the heading " Ethylene Amines” in Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 5, pp. 898-905 (Interscience Publishers, New York, 1950).
  • ethylene amine is used in a generic sense to denote a class of polyamines conforming for the most part to the structure H 2 N(CH 2 CH 2 NH) a H wherein a is an integer from 1 to 10
  • ethylene diamine diethylene triamine
  • triethylene tetraamine tetraethylene pentamine
  • pentaethylene hexamine pentaethylene hexamine
  • alkenyl succinimides are post-treated succinimides such as post-treatment processes involving ethylene carbonate disclosed by Wollenberg, et al., U.S. Patent No. 4,612,132 ; Wollenberg, et al., U.S. Patent No 4,746,446 ; as well as other post-treatment processes.
  • the dispersant component such as a polyalkylene succinimide, comprises from 2 to 40 weight percent, more preferably 5 to 20 weight percent and even more preferably 5 to 15 weight percent, of the weight of the oil dispersion of, hydrated alkali metal borate.
  • Polyalkylene succinic anhydrides or a non-nitrogen containing derivative of the polyalkylene succinic anhydride are also suitable dispersants for use in the compositions of this invention.
  • the polyalkylene succinic anhydride is preferably a polyisobutenyl succinic anhydride.
  • the polyalkylene succinic anhydride is a polyisobutenyl succinic anhydride having a number average molecular weight of at least 500, more preferably at least 900 to 3000 and still more preferably from at least 900 to 2300.
  • a mixture of polyalkylene succinic anhydrides is employed.
  • the mixture preferably comprises a low molecular weight polyalkylene succinic anhydride component and a high molecular weight polyalkylene succinic anhydride component. More preferably, the low molecular weight component has a number average molecular weight of from 500 to below 1000 and the high molecular weight component has a number average molecular weight of from 1000 to 3000.
  • both the low and high molecular weight components are polyisobutenyl succinic anhydrides
  • various molecular weights polyalkylene succinic anhydride components can be combined as a dispersant as well as a mixture of the other above referenced dispersants as identified above.
  • the polyalkylene succinic anhydride is the reaction product of a polyalkylene (preferably polyisobutene) with maleic anhydride.
  • a polyalkylene preferably polyisobutene
  • maleic anhydride One can use conventional polyisobutene, or high methylvinylidene polyisobutene in the preparation of such polyalkylene succinic anhydrides.
  • thermal PIBSA polyisobutenyl succinic anhydride
  • U.S. Patent No.3,361,673 chlorination PIBSA described in U.S. Patent No.
  • Patent Nos, 4,152,499 , 5,137,978 , and 5,137,980 high succinic ratio PIBSA made from high methylvinylidene polybutene described in European Patent Application Publication No. EP 355 895 ; terpolymer PIBSA described in U.S. Patent No. 5,792,729 ; sulfonic acid PIBSA described in U.S. Patent No. 5,777,025 and European Patent Application Publication No. EP 542 380 ; and purified PIBSA described in U.S. Patent No. 5,523,417 and European Patent Application Publication No. EP 602 863 .
  • the polyalkylene succinic anhydride or other dispersant component comprises from 2 to 40 weight percent, more preferably 5 to 20 weight percent, and even more preferably 5 to 15 weight percent, of the weight of the oil dispersion of hydrated alkali metal borate.
  • the hydrated alkali metal borate is in a ratio of at least 2:1 relative to the polyalkylene succinic anhydride or other dispersant, while preferably being in the range of 2:1 to 10:1. In a more preferred embodiment the ratio is at least 5:1 In another preferred embodiment, mixtures as defined above of the polyalkylene succinic anhydrides are employed.
  • the oil dispersion of hydrated alkali metal borate employed in the additive compositions of the present invention may optionally contain a detergent.
  • a detergent there are a number of materials that are suitable as detergents for the purpose of this invention These materials include phenates (high overbased or low overbased), high overbased phenate stearates, phenolates, salicylates, phosphonates, thiophosphonates and sulfonates and mixtures thereof.
  • sulfonates are used, such as high overbased sulfonates, low overbased sulfonates, or phenoxy sulfonates.
  • the sulfonic acids themselves can also be used.
  • the sulfonate detergent is preferably an alkali or alkaline earth metal salt of a hydrocarbyl sulfonic acid having from 15 to 200 carbons.
  • sulfonate encompasses the salts of sulfonic acid derived from petroleum products.
  • Such acids are well known in the art. They can be obtained by treating petroleum products with sulfuric acid or sulfur trioxide. The acids thus obtained are known as petroleum sulfonic acids and the salts as petroleum sulfonates. Most of the petroleum products which become sulfonated contain an oil-solubilizing hydrocarbon group.
  • sulfonate are the salts of sulfonic acids of synthetic alkyl aryl compounds.
  • These acids also are prepared by treating an alkyl aryl compound with sulfuric acid or sulfur trioxide. At least one alkyl substituent of the aryl ring is an oil-solubilizing group, as discussed above.
  • the acids thus obtained are known as alkyl aryl sulfonic acids and the salts as alkyl aryl sulfonates.
  • the sulfonates where the alkyl is straight-chain are the well-known linear alkylaryl sulfonates.
  • the acids obtained by sulfonation are converted to the metal salts by neutralizing with a basic reacting alkali or alkaline earth metal compound to yield the Group I or Group II metal sulfonates.
  • the acids are neutralized with an alkali metal base.
  • Alkaline earth metal salts are obtained from the alkali metal salt by metathesis.
  • the sulfonic acids can be neutralized directly with an alkaline earth metal base.
  • the sulfonates can then be overbased, although, for purposes of this invention, overbasing is not necessary. Overbased materials and methods of preparing such materials are well known to those skilled in the art. See, for example, LeSuer U.S. Pat. No. 3,496,105, issued Feb. 17, 1970 , particularly columns 3 and 4.
  • the sulfonates are present in the oil dispersion in the form of alkali and/or alkaline earth metal salts, or mixtures thereof.
  • the alkali metals include lithium, sodium and potassium.
  • the alkaline earth metals include magnesium, calcium and barium, of which the latter two are preferred.
  • salts of the petroleum sulfonic acids particularly the petroleum sulfonic acids which are obtained by sulfonating various hydrocarbon fractions such as lubricating oil fractions and extracts rich in aromatics which are obtained by extracting a hydrocarbon oil with a selective solvent, which extracts may, if desired, be alkylated before sulfonation by reacting them with olefins or alkyl chlorides by means of an alkylation catalyst; organic polysulfonic acids such as benzene disulfonic acid which may or may not be alkylated, and the like.
  • the preferred salts for use in the present invention are those of alkylated aromatic sulfonic acids in which the alkyl radical or radicals contain at least 8 carbon atoms, for example from 8 to 22 carbon atoms.
  • Another preferred group of sulfonate starting materials are the aliphatic-substituted cyclic sulfonic acids in which the aliphatic substituents or substituents contain a total of at least 12 carbon atoms, such as the alkyl aryl sulfonic acids, alkyl cycloaliphatic sulfonic acids, the alkyl heterocyclic sulfonic acids and aliphatic sulfonic acids in which the aliphatic radical or radicals contain a total of at least 12 carbon atoms.
  • oil-soluble sulfonic acids include petroleum sulfonic acids, mono- and poly-wax-substituted naphthalene sulfonic acids, substituted sulfonic acids, such as cetyl benzene sulfonic acids, cetyl phenyl sulfonic acids, and the like, aliphatic sulfonic acid, such as paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, etc., cycloaliphatic sulfonic acids, petroleum naphthalene sulfonic acids, cetyl cyclopentyl sulfonic acid, mono- and poly-wax-substituted cyclohexyl sulfonic acids, and the like.
  • the term "petroleum sulfonic acids” is intended to cover all sulfonic acids that are derived directly from petroleum products,
  • Typical Group II metal sulfonates suitable for use in the present invention include the metal sulfonates exemplified as follows: calcium white oil benzene sulfonate, barium white oil benzene sulfonate, magnesium white oil benzene sulfonate, calcium dipolypropene benzene sulfonate, barium dipolypropene benzene, sulfonate, magnesium dipolypropene benzene sulfonate, calcium mahogany petroleum sulfonate, barium mahogany petroleum sulfonate, magnesium mahogany.
  • the concentration of metal sulfonate that may be employed may vary over a wide range, depending upon the concentration of alkali metal borate particles When present, however, the detergent concentration will generally range from 0.2 to 10 weight percent and preferably from 3 to 7 weight percent, based on the total weight of the oil dispersion of the hydrated borate.
  • compositions of this invention may contain a mixture of both a metal sulfonate and an ashless dispersant, as described above, where the ratio is a factor of achieving the proper stability of the oil dispersion of the hydrated alkali metal borate.
  • the lubricating oil to which the hydrated alkali metal borate and the dispersant are added to form the oil dispersion of the hydrated alkali metal borate can be any hydrocarbon-based lubricating oil or a synthetic base oil stock.
  • these lubricating oils can be added to the oil dispersion of hydrated alkali metal borate and additive compositions containing them, as described herein, in additional amounts, to form finished oil compositions.
  • the hydrocarbon-based lubricating oils may be derived from synthetic or natural sources and may be paraffinic, naphthenic or aromatic base, or mixtures thereof.
  • the diluent oil can be natural or synthetic, and can be different viscosity grades.
  • the lubricating oil typically comprises from 30 to 70 weight percent, more preferably from 45 to 55 weight percent, based on the total weight of the oil dispersion of the hydrated alkali metal borate.
  • oil dispersion of hydrated alkali metal borate is present in the additive composition of the invention in the range of 10 to 90 weight percent, based on the total weight of the additive composition.
  • the additive composition of the present invention further contains an oil dispersion of hexagonal boron nitride.
  • Hexagonal boron nitride is a hexagonal, graphite-like form of boron nitride, having a layered structure and planar 6-membered rings of alternating boron and nitrogen atoms. On alternate sheets, boron atoms are directly over nitrogen atoms.
  • Hexagonal boron nitride can be prepared by heating boric oxide, boric acid or boric acid salts with ammonium chloride, alkali cyanides or calcium cyanamide at atmospheric pressure- Hexagonal boron nitride may also be prepared by the reaction of boron trichloride or boron trifluoride with ammonia.
  • a discussion of hexagonal boron nitride can be found, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, Vol. 4, pp. 427-429, John Wiley and Sons, New York, 1992 .
  • the oil dispersion of the hexagonal boron nitride will contain 1 to 50 weight percent of the hexagonal boron nitride, preferably 1 to 20 weight percent, and more preferably 5 to 15 weight percent, based on the total weight of the oil dispersion.
  • the oil dispersion of the hexagonal boron nitride will contain a surfactant as a stabilizer for the oil dispersion.
  • Typical surfactants for use as a stabilizer include ethylene propylene copolymers, or terpolymers of ethylene, propylene and an unconjugated dienes commonly known as ethylene-propylene-diene terpolymer, ethylene-propylene copolymers grafted with a nitrogen-containing vinyl functionality selected from the group consisting of N-vinyl pyrrollidone and N-vinyl pyridine, and the like.
  • the ethylene-propylene copolymer generally has an average molecular weight in the range of 22,000 to 200,000.
  • a preferred surfactant is, ethylene - propylene copolymer which has substantially equal proportions of ethylene and propylene monomers and an average molecular weight of from 22,000 to 40,000.
  • the surfactant concentration in the oil dispersion of hexagonal boron nitride will typically range from 0.1 to 25 weight percent, preferably from 2 to 7 weight percent, and more preferably from 3.0 to 5,0 weight percent, based on the total weight of the oil dispersion of hexagonal boron nitride.
  • the lubricant oil used to prepare the oil dispersion of the hexagonal boron nitride may be selected from the same group of natural or synthetic lubricating oils described above for use in preparing the oil dispersion of the hydrated alkali metal borate, but other carrier fluids have been found to be satisfactory, including vegetable oils such as rapeseed oil; liquid hydrocarbons such as aliphatic and aromatic naphthas and mixtures thereof; synthetic lubricant fluids such as polyalphaolefins, polyglycols, diester fluids, and mixtures of these liquids.
  • the oil used in forming the oil dispersion of hexagonal boron nitride may be the same as, or different from, the lubricant oil employed in preparing the oil dispersion of hydrated alkali metal borate.
  • Typical oils for preparing the oil dispersion of hexagonal boron nitride include the Group I and Group II base oils, such as 150 solvent neutral petroleum oil.
  • the oil dispersion of hexagonal boron nitride is present in the additive composition of the invention in the range of 10 to 90 weight percent, based on the total amount of the additive composition.
  • additive compositions of the present invention containing oil dispersions of alkali metal borate and hexagonal boron nitride may be blended further with additional additives to form additive packages containing the present additive compositions.
  • additive packages typically comprise from 10 to 80 weight percent of the additive composition of the present invention described above and from 90 to 20 weight percent of one or more of conventional additives selected from the group consisting of ashless dispersants (0-10%), detergents (0-5%), sulfurized hydrocarbons (0-40%), dialkyl hydrogen phosphates (0-15%), zinc dithiophosphates (0-20%), alkyl ammonium phosphates and/or thio- dithiophosphates (0-20%), phosphites (0 to 10%) fatty acid esters of polyalcohols (0-10%), 2,5-dimercaptothiadiazole (0-5%), benzotriazole (0-5%), dispersed molybdenum disulfide (0-5%), foam inhibitors (0-2%), and imidazo
  • Fully formulated finished oil compositions of this invention can be formulated from these additive packages upon further blending with an oil of lubricating viscosity.
  • the additive package described above is added to an oil of lubricating viscosity in an amount of from 1 to 20 weight percent, preferably 2 to 15 weight percent, to provide for the finished oil composition wherein the weight percent of the additive package is based on the total weight of the composition.
  • additives can be present in lubricating oils of the present invention. These additives include antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure agents, antifoam agents, other anti-wear agents, and a variety of other well-known additives in the art.
  • the additive composition of the present invention was evaluated in a lubricating oil for its anti-sticking properties following a test using an SAE No. 2 bench, which evaluates transmission fluids during synchronization.
  • the friction pairs used in this bench comprised a brass synchronizer ring and a steel gear cone
  • the cone is rotating, at a given speed, then the ring moves along the axis of the cone for its braking until it is blocked. At the end of each cycle, the ring is disengaged.
  • a sticking torque is measured when rotation of the cone is resumed.
  • the lubricating oil and the metal parts are heated to a temperature between about 60°C and 90°C.
  • the contact pressure is about 20 MPa and the initial sliding speed is 1.6 m/s.
  • an anti-sticking coefficient of 0 indicates the presence of cone on ring sticking during every cycle of the test. Conversely, an anti-sticking coefficient of 1 indicates no sticking at all was observed over the entire duration of the test. Thus the higher the anti-sticking coefficient, up to a maximum of 1, the better the anti-sticking performance of the lubricating oil.
  • test lubricating oil compositions were formulated as follows:
  • a lubricant composition was prepared containing the following:
  • the lubricant composition 2 was prepared containing the following:
  • the lubricant composition 3 was prepared containing the following:
  • a lubricating composition was prepared containing the following:
  • Lubricant Composition B (comparative )
  • a lubricating composition was prepared containing the following:

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Claims (17)

  1. Additivzusammensetzung für ein Getriebeöl, umfassend:
    (a) eine Öldispersion eines Alkalimetallborathydrats und
    (b) eine Öldispersion von hexagonalem Bornitrid;
    wobei das Gewichtsverhältnis von Alkalimetallborathydrat zu hexagonalem Bornitrid im Bereich von 95:5 bis 5:95 liegt.
  2. Additivzusammensetzung nach Anspruch 1, wobei es sich bei dem Alkalimetall in dem Alkalimetallborathydrat um Natrium oder Kalium handelt.
  3. Additivzusammensetzung nach Anspruch 2, wobei es sich bei dem Alkalimetall um Kalium handelt.
  4. Additivzusammensetzung nach Anspruch 3, wobei es sich bei dem Alkalimetallborathydrat um Kaliumtriborathydrat handelt.
  5. Additivzusammensetzung nach Anspruch 1, wobei die Öldispersion von Alkalimetallborathydrat ein Alkalimetallborathydrat, ein Dispergiermittel und ein Öl mit schmierender Viskosität enthält.
  6. Additivzusammensetzung nach Anspruch 5, wobei die Öldispersion von Alkalimetallborathydrat 10 bis 75 Gewichtsprozent des Alkalimetallborathydrats, bezogen auf das Gesamtgewicht der Öldispersion, enthält.
  7. Additivzusammensetzung nach Anspruch 5, wobei die Öldispersion von Alkalimetallborathydrat 2 bis 40 Gewichtsprozent des Dispergiermittels, bezogen auf das Gesamtgewicht der Öldispersion, enthält.
  8. Additivzusammensetzung nach Anspruch 5, wobei die Öldispersion von Alkalimetallborathydrat ferner ein Detergens enthält.
  9. Additivzusammensetzung nach Anspruch 8, wobei die Öldispersion von Alkalimetallborathydrat 0,2 bis 10 Gewichtsprozent des Detergens, bezogen auf das Gesamtgewicht der Öldispersion, enthält.
  10. Additivzusammensetzung nach Anspruch 1, wobei die Öldispersion von Alkalimetallborathydrat in der Additivzusammensetzung in einer Menge von 10 bis 90 Gewichtsprozent, bezogen auf das Gesamtgewicht der Additivzusammensetzung, vorliegt.
  11. Additivzusammensetzung nach Anspruch 1, wobei das hexagonale Bornitrid eine Teilchengrößenverteilung aufweist, bei der mindestens 90% der Teilchen eine Größe von weniger als etwa 0,5 Mikron aufweisen.
  12. Additivzusammensetzung nach Anspruch 1, wobei die Öldispersion von hexagonalem Bornitrid ein Öl mit schmierender Viskosität und 1 bis etwa 50 Gewichtsprozent hexagonales Bornitrid, bezogen auf das Gesamtgewicht der Öldispersion, enthält.
  13. Additivzusammensetzung nach Anspruch 12, wobei die Öldispersion von hexagonalem Bornitrid ferner ein Tensid als Stabilisator enthält.
  14. Additivzusammensetzung nach Anspruch 1, wobei die Öldispersion von hexagonalem Bornitrid in der Additivzusammensetzung in einer Menge von 10 bis 90 Gewichtsprozent, bezogen auf das Gesamtgewicht der Additivzusammensetzung, vorliegt.
  15. Schmierölzusammensetzung, enthaltend eine Hauptmenge eines Getriebeöls mit schmierender Viskosität und eine wirksame synchronisiereinrichtungsverklebungsverringernde Menge einer Additivzusammensetzung, umfassend:
    (a) eine Öldispersion eines Alkalimetallborathydrats und
    (b) eine Öldispersion von hexagonalem Bornitrid;
    wobei das Gewichtsverhältnis von Alkalimetallborathydrat zu hexagonalem Bornitrid im Bereich von 95:5 bis 5:95 liegt.
  16. Schmierölzusammensetzung nach Anspruch 15, wobei die Schmierölzusammensetzung 1 bis 20 Gewichtsprozent der Additivzusammensetzung, bezogen auf das Gesamtgewicht der Schmierölzusammensetzung, enthält.
  17. Schmierölzusammensetzung nach Anspruch 15, wobei es sich bei dem Getriebeöl um ein Schaltgetriebeöl handelt.
EP02291928A 2002-07-30 2002-07-30 Hydratisiertes Alkalimetallborat und hexagonales Bornitrid enthaltende Additivzusammensetzung für Getriebeöle Expired - Lifetime EP1386956B1 (de)

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ES02291928T ES2329446T3 (es) 2002-07-30 2002-07-30 Composicion aditiva para aceite de transmision que contienen un borato de metal alcalino hidratado y nitruro de boro hexagonal.
AT02291928T ATE435268T1 (de) 2002-07-30 2002-07-30 Hydratisiertes alkalimetallborat und hexagonales bornitrid enthaltende additivzusammensetzung für getriebeöle
EP02291928A EP1386956B1 (de) 2002-07-30 2002-07-30 Hydratisiertes Alkalimetallborat und hexagonales Bornitrid enthaltende Additivzusammensetzung für Getriebeöle
DE60232788T DE60232788D1 (de) 2002-07-30 2002-07-30 Hydratisiertes Alkalimetallborat und hexagonales Bornitrid enthaltende Additivzusammensetzung für Getriebeöle
US10/624,240 US20040147409A1 (en) 2002-07-30 2003-07-22 Additive composition for transmission oil containing hydrated alkali metal borate and hexagonal boron nitride
JP2004525416A JP4391937B2 (ja) 2002-07-30 2003-07-28 水和アルカリ金属ホウ酸塩と六方晶系窒化ホウ素を含む変速機油用添加剤組成物
CA2493288A CA2493288C (en) 2002-07-30 2003-07-28 Additive composition for transmission oil containing hydrated alkali metal borate and hexagonal boron nitride
AU2003260447A AU2003260447A1 (en) 2002-07-30 2003-07-28 Additive composition for transmission oil containing hydrated alkali metal borate and hexagonal boron nitride
PCT/EP2003/009312 WO2004013262A1 (en) 2002-07-30 2003-07-28 Additive composition for transmission oil containing hydrated alkali metal borate and hexagonal boron nitride
US11/999,712 US20080153724A1 (en) 2002-07-30 2007-12-04 Additive composition for transmission oil containing hydrated alkali metal borate and hexagonal boron nitride
US13/416,392 US20120172264A1 (en) 2002-07-30 2012-03-09 Additive Composition for Transmission Oil Containing Hydrated Alkali Metal Borate and Hexagonal Boron Nitride

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EP02291928A EP1386956B1 (de) 2002-07-30 2002-07-30 Hydratisiertes Alkalimetallborat und hexagonales Bornitrid enthaltende Additivzusammensetzung für Getriebeöle

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AU (1) AU2003260447A1 (de)
CA (1) CA2493288C (de)
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US6534450B1 (en) * 2001-09-28 2003-03-18 Chevron Oronite Company Llc Dispersed hydrated sodium borate compositions having improved properties in lubricating oil compositions
PT1535987E (pt) * 2003-11-28 2013-03-04 Total Raffinage Marketing Composição de aditivo para óleo de transmissão contendo nitreto de boro hexagonal e um melhorador do índice de viscosidade

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CA2493288C (en) 2011-11-15
WO2004013262A1 (en) 2004-02-12
AU2003260447A1 (en) 2004-02-23
US20040147409A1 (en) 2004-07-29
ATE435268T1 (de) 2009-07-15
US20080153724A1 (en) 2008-06-26
DE60232788D1 (de) 2009-08-13
EP1386956A1 (de) 2004-02-04
CA2493288A1 (en) 2004-02-12
US20120172264A1 (en) 2012-07-05
AU2003260447A8 (en) 2004-02-23
JP2005534762A (ja) 2005-11-17
WO2004013262A8 (en) 2004-05-21
ES2329446T3 (es) 2009-11-26
JP4391937B2 (ja) 2009-12-24

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