EP1910505B1 - Zinkfreies ackerschlepperfluid - Google Patents

Zinkfreies ackerschlepperfluid Download PDF

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Publication number
EP1910505B1
EP1910505B1 EP06785653.4A EP06785653A EP1910505B1 EP 1910505 B1 EP1910505 B1 EP 1910505B1 EP 06785653 A EP06785653 A EP 06785653A EP 1910505 B1 EP1910505 B1 EP 1910505B1
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EP
European Patent Office
Prior art keywords
percent
weight
fatty
oil
compound
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.)
Revoked
Application number
EP06785653.4A
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English (en)
French (fr)
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EP1910505A2 (de
Inventor
David E. Ripple
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
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Lubrizol Corp
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Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP1910505A2 publication Critical patent/EP1910505A2/de
Application granted granted Critical
Publication of EP1910505B1 publication Critical patent/EP1910505B1/de
Revoked legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • 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
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
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    • 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
    • C10M2207/126—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 monocarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
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    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
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    • 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
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    • 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
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08—Amides
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    • C10M2215/28—Amides; Imides
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
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    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
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    • 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
    • C10M2223/042—Metal salts thereof
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
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    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
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    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
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    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
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    • C10N2030/76—Reduction of noise, shudder, or vibrations
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to a method of using lubricants for farm tractor fluids, also referred to as tractor hydraulic fluids or lubricants.
  • the fluids are substantially free from zinc salts such as zinc dialkyldithiophosphates.
  • Farm tractor lubricants are fluids which are called upon to play multiple roles in the lubrication of farm tractors and related equipment. In many instances the same fluid is used to lubricant the crankcase, clutch, transmission, and power take-off components. As a result of exposure to the harsh conditions of the crankcase, the fluid may become contaminated with water and other byproducts of combustion.
  • lubricants in general and farm tractor lubricants in particular have contained zinc dialkyldithiophosphates ("ZDPs") as important components, providing antioxidancy, anti-corrosion activity, antiwear activity and other benefits.
  • ZDPs zinc dialkyldithiophosphates
  • exposure of such lubricants to water during use can lead to hydrolysis of the ZDP as well as other interactions with metals such as copper and consequent loss of, e.g., corrosion protection for yellow metals.
  • tractor hydraulic fluids there are many formulations that have been suggested for use as farm tractor fluids, also known as tractor hydraulic fluids.
  • U.S. Patent 5,843,873, Butke et al., December 1, 1998 discloses lubricants and fluids useful in pressure transmitting applications such as tractor hydraulic fluids.
  • the compositions contain a thiocarbamate and a phosphorus acid or ester or an amine salt thereof, an a surfactant which can be, e.g., glycerol partial esters.
  • the phosphorus compound can be a dialkyl hydrogen phosphite.
  • Another additive which can be present is a dimercaptothiadiazole or a derivative thereof, which can be used as a copper corrosion inhibitor.
  • Overbased materials can also be present, which can be further treated, if desired with other substances such as a boron source.
  • European Patent Application Publication EP 0 712 924 A discloses oil based compositions which can serve as a functional fluid, in particular, a tractor hydraulic fluid.
  • a surfactant can also be present.
  • the materials are described as providing good antiwear properties even in the absence of typical zinc compounds such as zinc dialkylthiophosphates.
  • Another additive which can be present is a dimercaptothiadiazole or a derivative thereof, which can be used as a copper corrosion inhibitor.
  • Among the listed surfactants is a borated C 16 ⁇ -olefin epoxide.
  • U.S. Patent 5,284,591, Bayles et al., February 8, 1994 discloses a functional fluid (one type of which is a tractor fluid) comprising an overbased calcium sulfonate, a ZDP, a borated epoxide, a carboxylic solubilizer in the form of an ester-salt reaction product of an acylating agent and an alkanol tertiary monoamine, and a sulfurized composition.
  • U.S. Patent 5,635,459 discloses borated overbased sulfonates for improved gear performance in functional fluids.
  • the fluid can also contain a ZDP or other EP/antiwear agent, and a borated epoxide.
  • Functional fluids are disclosed to include tractor fluids.
  • U.S. Patent 5,298,177, Stoffa, March 29, 1994 discloses a functional fluid comprising a triglyceride, a detergent-inhibitor additive, a viscosity modifying additive, and a synthetic oil.
  • the detergent inhibitor can be free from phosphorus and zinc and can include, e.g., a metal passivator which can be an oil-soluble derivative of a dimercaptothiadiazole.
  • the detergent inhibitor may also be a borated complex of an overbased metal sulfonate, carboxylate, or phenate.
  • Patent 5,767,044 discloses lubricating composition
  • lubricating composition comprising a major amount of an oil of lubricating viscosity, (A) an hydrocarbyl phosphite, wherein each hydrocarbyl group is saturated and independently contains from about 12 to about 28 carbon atoms, (B) an organic polysulfide wherein the organic polysulfide, is a sulfurized member selected from the group consisting of oils, fatty acids or esters, olefins, and polyolefms, and (C) (i) a borated overbased salt of an acidic organic compound, (ii) a combination of a borated dispersant and a phosphorus antiwear or extreme pressure agent selected from the group consisting of a salt of phosphoric acid ester, a lower alkyl phosphite, and a phosphorus-containing carboxylic acid, ester, ether, or amide, or (iii) a mixture of (i) and (i
  • the present invention solves the problem of hydrolysis of ZDP and resulting deterioration in performance by providing a fluid free from or substantially free from ZDP and other zinc compounds, by including a dithiophosphate ester or salt (other than zinc), a heterocyclic organic compound, and a boron-containing component.
  • the fluid of the invention continues to exhibit acceptable performance.
  • the absence of ZDP can also provide a fluid with improved environmental properties.
  • the present invention therefore provides a method for lubricating the hydraulic system of a farm tractor, comprising supplying thereto a lubricating composition comprising:
  • One component of the composition used in the present invention is an oil of lubricating viscosity, which can be present in a major amount, for a lubricant composition, or in a concentrate forming amount, for a concentrate.
  • Suitable oils include natural and synthetic lubricating oils and mixtures thereof.
  • the oil of lubricating viscosity is generally present in a major amount (i.e. an amount greater than 50 percent by weight).
  • the oil of lubricating viscosity is present in an amount of 75 to 95 percent by weight, and often greater than 80 percent by weight of the composition.
  • Natural oils useful in making the lubricants and functional fluids include animal oils and vegetable oils as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic/-naphthenic types which may be further refined by hydrocracking and hydrofinishing processes.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, also known as polyalphaolefins; polyphenyls; alkylated diphenyl ethers; alkyl- or dialkylbenzenes; and alkylated diphenyl sulfides; and the derivatives, analogs and homologues thereof. Also included are alkylene oxide polymers and interpolymers and derivatives thereof, in which the terminal hydroxyl groups may have been modified by esterification or etherification.
  • esters of dicarboxylic acids with a variety of alcohols or esters made from C5 to C12 monocarboxylic acids and polyols or polyol ethers.
  • Other synthetic oils include silicon-based oils, liquid esters of phosphorus-containing acids, and polymeric tetrahydrofurans.
  • Unrefined, refined and rerefined oils can be used in the lubricants used in the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Refined oils have been further treated in one or more purification steps to improve one or more properties. They can, for example, be hydrogenated, resulting in oils of improved stability against oxidation.
  • the oil of lubricating viscosity is an API Group II, Group III, Group IV, or Group V oil, including a synthetic oil, or mixtures thereof. These are classifications established by the API Base Oil Interchangeability Guidelines. Both Group II and Group III oils contain ⁇ 0.03 percent sulfur and > 99 percent saturates. Group II oils have a viscosity index of 80 to 120, and Group III oils have a viscosity index > 120. Polyalphaolefins are categorized as Group IV. The oil can also be an oil derived from hydroisomerization of wax such as slack wax or a Fischer-Tropsch synthesized wax. Group V is encompasses "all others" (except for Group I, which contains > 0.03% S and/or ⁇ 90% saturates and has a viscosity index of 80 to 120).
  • At least 50% by weight of the oil of lubricating viscosity is a polyalphaolefin (PAO).
  • PAO polyalphaolefin
  • the polyalphaolefins are derived from monomers having from 4 to 30, or from 4 to 20, or from 6 to 16 carbon atoms.
  • Examples of useful PAOs include those derived from 1-decene. These PAOs may have a viscosity of 1.5 to 150 mm 2 /s (cSt) at 100°C.
  • PAOs are typically hydrogenated materials.
  • the oils used in the present invention can encompass oils of a single viscosity range or a mixture of high viscosity and low viscosity range oils.
  • the oil exhibits a 100°C kinematic viscosity of 1 or 2 to 8 or 10 mm 2 /sec (cSt).
  • the overall lubricant composition is preferably formulated using oil and other components such that the viscosity at 100°C is 1 or 1.5 to 10 or 15 or 20 mm 2 /sec and the Brookfield viscosity (ASTM-D-2983) at -40°C is less than 20 or 15 Pa-s (20,000 cP or 15,000 cP), or less than 10 Pa-s, or even 5 or less.
  • the invention includes use of an amine salt of a phosphorus acid ester.
  • This material can serve as one or more of an extreme pressure agent, a wear preventing agent.
  • the amine salt of a phosphorus acid ester includes phosphoric acid esters and salts thereof; dialkyldithiophosphoric acid esters and salts thereof; phosphites; and phosphorus-containing carboxylic esters, ethers, and amides; and mixtures thereof.
  • the phosphorus compound further comprises a sulfur atom in the molecule.
  • the amine salt of the phosphorus compound is ashless, i.e., metal-free (prior to being mixed with other components).
  • the amine salt of the phosphorus acid ester may comprise any of a variety of chemical structures.
  • a variety of structures are possible when the phosphorus acid ester compound contains one or more sulfur atoms, that is, when the phosphorus-containing acid is a thiophosphorus acid ester.
  • the thiophosphorus acid esters may be mono- or dithiophosphorus acid esters.
  • Thiophosphorus acid esters are also sometimes referred to as thiophosphoric acids.
  • a phosphorus acid ester may be prepared by reacting a phosphorus compound with an alcohol.
  • Suitable phosphorus compound include phosphorus pentoxide, phosphorus trioxide, phosphorous tetroxide, phosphorus acids, phosphorus esters, and phosphorus sulfides such as phosphorus pentasulfide.
  • Suitable alcohols include those containing up to 30 or to 24, or to 12 carbon atoms, including primary or secondary alcohols such as isopropyl, butyl, amyl, s-amyl, 2-ethylhexyl, hexyl, cyclohexyl, octyl, decyl and oleyl alcohols, as well as any of a variety of commercial alcohol mixtures having, e.g., 8 to 10, 12 to 18, or 18 to 28 carbon atoms. Polyols such as diols may also be used.
  • the phosphorus acid ester is a monothiophosphoric acid ester or a monothiophosphate.
  • Monothiophosphates may be prepared by the reaction of a sulfur source with a dihydrocarbyl phosphite.
  • the sulfur source may, for instance, be elemental sulfur, or an organosufide, such as a sulfur coupled olefin or a sulfur coupled dithiophosphate.
  • the preparation of monothiophosphates is disclosed in U.S. Patent 4,755,311 and PCT Publication WO 87/07638 , which describe monothiophosphates, sulfur sources, and the process for making monothiophosphates.
  • Monothiophosphates may also be formed in the lubricant blend by adding a dihydrocarbyl phosphite to a lubricating composition containing a sulfur source, such as a sulfurized olefin.
  • a sulfur source such as a sulfurized olefin.
  • the phosphite may react with the sulfur source under blending conditions (i.e., temperatures from about 30°C to about 100°C or higher) to form the monothiophosphate salt with an amine which is present in the blend.
  • the phosphorus-containing acid is a dithiophosphoric acid or phosphorodithioic acid.
  • the dithiophosphoric acid may be represented by the formula (RO) 2 PSSH wherein each R is independently a hydrocarbyl group containing 3 to 30 carbon atoms. R generally contains up to 18, or to 2, or to 8 carbon atoms.
  • R examples include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl, n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and tridecyl groups.
  • Illustrative lower alkylphenyl R groups include butylphenyl, amylphenyl, and heptylphenyl.
  • mixtures of R groups include 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl, and isooctyl.
  • the dithiophosphoric acid may be reacted with an epoxide or a glycol and this reaction product further reacted with a phosphorus acid, anhydride, or lower ester.
  • the epoxide is generally an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, and styrene oxide.
  • the glycols may be aliphatic glycols having from 1 to 12, or 2 to 6, or 2 or 3 carbon atoms.
  • the dithiophosphoric acids, glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same are described in U.S. Patents 3,197,405 and 3,544,465 .
  • Example B-1 Phosphorus pentoxide (about 64 grams) is added at about 58°C over a period of about 45 minutes to about 514 grams of hydroxypropyl O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting di(4-methyl-2-pentyl)-phosphorodithioic acid with about 1.3 moles of propylene oxide at about 25°C).
  • the mixture is heated at about 75°C for about 2.5 hours, mixed with a diatomaceous earth and filtered at about 70°C.
  • the filtrate contains about 11.8% by weight phosphorus, about 15.2% by weight sulfur, and an acid number of 87 (bromophenol blue).
  • Example B-2 A mixture of about 667 grams of phosphorus pentoxide and the reaction product of about 3514 grams of diisopropyl phosphorodithioic acid with about 986 grams of propylene oxide at about 50°C is heated at about 85°C for about 3 hours and filtered. The filtrate contains about 15.3% by weight phosphorus, about 19.6% by weight sulfur, and an acid number of 126 (bromophenol blue).
  • Acidic phosphoric acid esters may be reacted with ammonia or an amine, including polyamines, to form an ammonium salt.
  • the salts may be formed separately and then the salt of the phosphorus acid ester may be added to the lubricating composition. Alternately, the salts may also be formed in situ when the acidic phosphorus acid ester is blended with other components to form a fully formulated lubricating composition.
  • the amines which may be suitable for use as the amine salt include primary amines, secondary amines, tertiary amines, and mixtures thereof.
  • the amines include those with at least one hydrocarbyl group, or, in certain embodiments, two or three hydrocarbyl groups.
  • the hydrocarbyl groups may typically contain 2 to 30 carbon atoms, or in another embodiments 8 to 26 or 10 to 20 or 13 to 19 carbon atoms.
  • Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, as well as such fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleyamine.
  • fatty amines include commercially available fatty amines such as "Armeen®” amines (products available from Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
  • suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine and ethylamylamine.
  • the secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
  • the amine may also be a tertiary-aliphatic primary amine.
  • the aliphatic group in this case may be an alkyl group containing 2 to 30, or 6 to 26, or 8 to 24 carbon atoms.
  • Tertiary alkyl amines include monoamines such as tert-butylamine, tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine, tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
  • amines may also be used in the invention.
  • a useful mixture of amines is "Primene® 81R” and “Primene® JMT.”
  • Primene® 81R and Primene® JMT are mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines respectively.
  • Suitable hydrocarbyl amine salts of alkylphosphoric acid of the invention may be represented by the following formula: wherein R 21 and R 22 are independently hydrogen or hydrocarbyl groups such as alkyl groups; for the phosphorus acid ester, at least one of R 21 and R 22 will be hydrocarbyl.
  • R 21 and R 22 may contain 3 or 4 to 30, or 8 to 25, or 10 to 20, or 13 to 19 carbon atoms.
  • R 23 , R 24 and R 25 can be independently hydrogen or hydrocarbyl groups, such as alkyl branched or linear alkyl chains with 1 to 30, or 4 to 24, or 6 to 20, or 10 to 16 carbon atoms.
  • R 23 , R 24 and R 25 groups can be branched or linear groups, and in certain embodiments at least one, or alternatively two of R 23 , R 24 and R 25 are hydrogen.
  • alkyl groups suitable for R 23 , R 24 and R 25 include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl groups and mixtures thereof.
  • the hydrocarbyl amine salt of an alkylphosphoric acid ester is the reaction product of a C 14 to C 18 alkylated phosphoric acid with Primene 81RTM (produced and sold by Rohm & Haas) which is a mixture of C 11 to C 14 tertiary alkyl primary amines.
  • Primene 81RTM produced and sold by Rohm & Haas
  • Other amines which may be used include alkyl alkanol amines, dialkanolamines, trialkanolamines such as triethanolamines as well as borated amines as described hereinbelow.
  • hydrocarbyl amine salts of dialkyldithiophosphoric acid esters of the invention may be represented by the formula: wherein the various R groups are as defined above and R 26 and R 27 are as defined for R 21 and R 22 . In some embodiments R 26 and R 27 are both hydrocarbyl groups, and they may contain 3 carbon atoms.
  • hydrocarbyl amine salts of dialkyldithiophosphoric acid esters include the reaction product(s) of heptylated or octylated or nonylated dithiophosphoric acids with ethylene diamine, morpholine, or Primene 81RTM, and mixtures thereof.
  • the amine salt as used as this component in the present invention may thus comprise a C 8 to C 20 alkylamine salt of a mono- or di-alkyl phosphate ester, or mixtures thereof.
  • the amount of the amine salt of the phosphorus acid ester is 0.04 to 4 percent by weight of the lubricating composition, or it can be 0.1 to 2, or 0.2 to 1, or 0.3 to 0.8, or 0.4 to 0.5 weight percent. The amounts will be proportionally higher in a concentrate.
  • thiadiazole compound Another material useful in the present invention is thiadiazole compound.
  • This material may, but need not necessarily, serve as a copper corrosion inhibitor, and it is sometimes referred to as such herein.
  • examples of such materials include dimercaptothiadozoles ("DMTD") which may typically serve as a metal passivator and/or an anti-wear agent.
  • DMTDs dimercaptothiadozoles
  • their preparation are described in greater detail in U.S. Patent 5,298,177 , see columns 42 through 47.
  • the dimercaptothiadiazoles which can be utilized in the present invention typically are soluble forms or derivatives of DMTD.
  • Materials which can be starting materials for the preparation of oil-soluble derivatives containing the dimercaptothiadiazole nucleus can include 2,5-dimercapto-[1,3,4]-thiadiazole, 3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole, and 4,-5-dimercapto-[1,2,3]-thiadaizole. Of these the most readily available is 2,5-dimercapto-[1,3,4]-thiadiazole.
  • DMTDs are conveniently prepared by the reaction of one mole of hydrazine, or a hydrazine salt, with two moles of carbon disulfide in an alkaline medium, followed by acidification.
  • a hydrazine salt for the preparation of oil-soluble derivatives of DMTD, it is possible to utilize already prepared DMTD or to prepare the DMTD in situ and subsequently adding a material to be reacted with DMTD.
  • U.S. Patents 2,719,125 ; 2,719,126 ; and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles and 2-hydrocarbyldithio-5-mercapto-[1,3,4]-thiadiazoles.
  • the hydrocarbon group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl.
  • Such polysulfides can be represented by the following general formula wherein R and R' may be the same or different hydrocarbyl groups which may, generally, be as defined for the R groups of the above hydrocarbyl amine salts, and x and y be integers from 0 to 8, and the sum of x and y is at least 1. Alternatively, in certain embodiments, R' can be H when y is 0.
  • a process for preparing such derivatives is described in U.S. Pat. No. 2,191,125 , comprising reacting DMTD with a suitable sulfenyl chloride or by reacting the dimercapto diathiazole with chlorine and reacting the resulting disulfenyl chloride with a primary or tertiary mercaptan.
  • U.S. Pat. No. 3,087,932 further describes a one-step process for preparing 2,5-bis (hydrocarbyldithio)-1, 3,4-thiadiazole.
  • carboxylic esters of DMTD are described in U.S. Pat. No. 2,760,933 .
  • condensation products of alpha-halogenated aliphatic monocarboxylic acids having at least 10 carbon atoms with DMTD are described in U.S. Pat. No. 2,836,564
  • U.S. Pat. No. 2,765,289 describes products obtained by reacting DMTD with an aldehyde and a diaryl amine in molar proportions of from about 1:1:1 to about 1:4:4.
  • the DMTD materials may also be present as salts such as amine salts. Further derivatives are also described in greater detail in the aforementioned US Patent 5,298,177 .
  • the thiazole compound may be the reaction product of a phenol with an aldehyde and a dimercaptothiadiazole.
  • the phenol may be an alkyl phenol wherein the alkyl group contains at least about 6, e.g., 6 to 24, or 6, or 7, to 12 carbon atoms.
  • the aldehyde may be an aldehyde containing 1 to 7 carbon atoms or an aldehyde synthon, such as formaldehyde. In one embodiment, the aldehyde is formaldehyde or paraformaldehyde.
  • the aldehyde, phenol and dimercaptothiadiazole are typically reacted by mixing them at a temperature up to about 150°C such as 50°C to 130°C, in molar ratios of 0.5 to 2 moles of phenol and 0.5 to 2 moles of aldehyde per mole of dimercaptothiadiazole.
  • the three reagents are reacted in equal molar amounts.
  • the product may be described as an alkylhydroxyphenylmethylthio-substituted [1,3,4]-thiadiazole; the alkyl moiety may be, among others, hexyl, heptyl, octyl, or nonyl.
  • Useful thiadaizole compounds thus may include 2-alkyldithio-5-mercapto-[1,3,4]-thiadiazoles, 2,5-bis(alkyldithio)-[1,3,4]-thiadiazoles, 2-alkylhydroxyphenylmethylthio-5-mercapto-[1,3,4]-thiadiazoles, and mixtures thereof.
  • DMTD derivative is obtained by reacting DMTD with an oil-soluble dispersant, such as a substantially neutral or acidic carboxylic dispersant, e.g., a succinimide dispersant or a succinic ester dispersant, in a diluent, by heating the mixture above about 100°C.
  • an oil-soluble dispersant such as a substantially neutral or acidic carboxylic dispersant, e.g., a succinimide dispersant or a succinic ester dispersant
  • the amount of the thiadiazole copper corrosion inhibitor is 0.01 to 5 percent by weight of the composition, depending in part on the identity of the particular compound. For instance, if the thiadiazole compound is as described for the structure shown above, the amount may be 0.01 to 1 percent, or 0.02 to 0.4 or 0.03 to 0.1 percent by weight. Alternatively, if the thiadiazole is reacted with a nitrogen-containing dispersant, the total weight of the combined product may be significantly higher in order to impart the same active thiadiazole chemistry; for instance, 0.1 to 5 percent, or 0.2 to 2 or 0.3 to 1 or 0.4 to 0.6 percent by weight. The amounts will be proportionally higher in a concentrate.
  • Another component useful in the present invention is a detergent.
  • Detergents as used herein are metal salts of organic acids and are well-known from such publications as US 2004-0102335 and references cited therein.
  • the organic acid portion of the detergent is typically a sulfonate, carboxylate, phenate, salicylate, or salixarate.
  • the metal portion of the detergent is typically an alkali or alkaline earth metal. Suitable metals include sodium, calcium, potassium and magnesium.
  • Suitable overbased organic salts include sulfonate salts having a substantially oleophilic character and which are formed from organic materials.
  • Organic sulfonates are well known materials in the lubricant and detergent arts.
  • the sulfonate compound can contain on average 10 to 40 carbon atoms, for instance, 12 to 36 carbon atoms or 14 to 32 carbon atoms.
  • the phenates, salicylates, salixarates, and carboxylates have a substantially oleophilic character.
  • the present invention allows for the carbon atoms to be either aromatic or in paraffinic configuration, it is common that alkylated aromatics be employed. While naphthalene based materials may be employed, the aromatic material is typically based on benzene.
  • compositions thus include overbased monosulfonated alkylated benzene, such as monoalkylated benzene.
  • alkyl benzene fractions are obtained from still bottom sources and are mono- or di-alkylated.
  • a mixture of mono-alkylated aromatics are utilized to obtain the mono-alkylated salt (benzene sulfonate).
  • Mixtures wherein a substantial portion of the composition contains polymers of propylene as the source of the alkyl groups can also be used to assist in the solubility of the salt.
  • mono-functional (e.g., mono-sulfonated) materials can be used to avoid crosslinking of the molecules with less precipitation of the salt from the lubricant.
  • the detergents are typically "overbased.” By overbasing, it is meant that a stoichiometric excess of the metal is present over that required to neutralize the anion of the salt, typically facilitated by the addition of carbon dioxide.
  • the excess metal from overbasing has the effect of neutralizing acids which may build up in the lubricant, as well as increasing the dynamic coefficient of friction.
  • the excess metal will be present over that which is required to neutralize the anion at in the ratio of up to 30:1, such as 1.5:1 to 20:1 or 5:1 to 18:1 on an equivalent basis.
  • the amount of the overbased metal detergent used in the composition is 0.05 to 6 weight percent on an oil free basis, for instance, 0.1 to 2 percent or 0.2 to 1.0 percent, or in other embodiments 1 to 5 percent or 2 to 4 percent.
  • the overbased salt as supplied often includes 40% to 50% diluent oil and with a total base number (TBN) of 10 to 600 or to 800 on an oil free basis, or a proportionally lower TBN when calculated including the diluent oil.
  • TBN total base number
  • the detergent can be post-treated with such agents as borating agents. Borated and non-borated overbased detergents are also described in U.S. Patents 5,403,501 and 4,792,410 and references cited therein.
  • boron compound Another component useful in the present invention is a boron compound.
  • the boron compound should be soluble or dispersible in the lubricating compositions.
  • the boron compound is also to be considered and accounted for separately from any borated detergent, described above.
  • the actual chemical identity of the boron compound can be quite diverse. Suitable materials include borated fatty epoxides, known from Canadian Patent No. 1,188,704 .
  • These oil-soluble boron- containing compositions can be prepared by reacting boric acid (in any of its various forms) or boron trioxide with at least a fatty epoxide of the general formula wherein the R groups are hydrogen or aliphatic radicals or which may together form cyclic groups.
  • the fatty epoxide generally contains at least 8 carbon atoms to provide a measure of oil solubility. These materials are often referred to as borated epoxides, and they are described in detail in U.S. Pat. No. 4,584,115 . These are generally prepared by reacting an epoxide with boric acid or boron trioxide. Borated epoxides thus are not themselves epoxides but are the boron-containing reaction products of epoxides.
  • the epoxides can be, for example, commercial mixtures of C 14-16 or C 14-18 epoxides, which can be purchased from Elf-Atochem or Union Carbide and which can be prepared, in turn, from the corresponding olefins by known methods.
  • Purified epoxy compounds such as 1,2-epoxyhexadecane can be purchased from Aldrich Chemicals.
  • the borated epoxides are prepared by blending the boron source and the epoxide and heating until the desired reaction has occurred.
  • One suitable borated epoxide is the borated epoxide of a predominantly 16 carbon olefin.
  • borate esters can be employed, such as are known in the art and described, for instance, in U.S. patent 5,883,057 and U.S. patent application 2005 0014656 .
  • Such borate esters may be prepared by reacting of one or more boron compounds with one or more alcohols. In some embodiments the alcohols contain 6 to 30, or 8 to 24 carbon atoms.
  • the borate esters may be of various formulas including (RO) 3 B or (RO) 2 B-O-B(OR) 2 or wherein each R is independently hydrogen or a hydrocarbyl group containing 2 to 24 carbon atoms, provided that at least one R is a hydrocarbyl group.
  • the R groups may also be aliphatic groups of 4 to 6 carbon atoms and in one embodiment all the R groups are aliphatic groups.
  • suitable trihydrocarbyl borates are triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tripentyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, triisooctyl borate, tridecyl borate, tri (C 8-10 ) borate, tri (C 12-15 borate) and oleyl borate.
  • the borate esters can be prepared by reacting 1 to 3 moles of alcohol ROH with 1 mole of orthoboric acid H 3 BO 3 , typically at a temperature of above 100°C in order to remove of water of condensation.
  • the length of the alkyl groups in any such borate esters can be varied to obtain desired performance, e.g., solubility or lubricity.
  • partial borate esters can be used.
  • Organic borate salts can also be used.
  • Suitable boron compounds also include borated amines, which are generally known from U.S. Patent 4,622,158 .
  • Borated amines (including borated alkoxylated fatty amines) are conveniently prepared by the reaction of a boron compound, as described above, with the corresponding amines.
  • the amine can be a simple fatty amine or a hydroxy-containing amine.
  • Among the amines useful in preparing the borated amines are commercial alkoxylated fatty amines known by the trademark EthomeenTM and available from Akzo Nobel.
  • EthomeenTM C/12 bis[2-hydroxyethyl]-coco-amine
  • EthomeenTM C/20 polyoxyethylene[10]cocoamine
  • EthomeenTM S/12 bis[2-hydroxyethyl]soyamine
  • EthomeenTM T/12 bis[2-hydroxyethyl]-tallow-amine
  • EthomeenTM T/15 polyoxyethylene-[5]tallowamine
  • EthomeenTM 0/12 bis[2-hydroxyethyl]oleyl-amine
  • EthomeenTM 18/12 bis[2-hydroxyethyl]octadecylamine
  • EthomeenTM 18/25 polyoxyethyl-ene[15]-octadecylamine
  • Fatty amines and ethoxylated fatty amines are also described in U.S. Patent 4,741,848 .
  • the boron compound can also be a borated fatty acid ester, e.g., a borated fatty ester of glycerol.
  • a borated fatty acid ester of glycerol e.g., borated fatty ester of glycerol.
  • Such material can be prepared by borating a fatty acid ester of glycerol with boric acid with removal of the water of reaction.
  • the boron compound is a borated dispersant, such as a borated nitrogen-containing dispersant.
  • a borated dispersant contains 0.1% to 5%, or 0.5% to 4%, or 0.7% to 3% by weight boron.
  • the borated dispersant is a borated acylated amine, such as a borated succinimide dispersant. Borated dispersants are described in U.S. Pat. Nos. 3,000,916 ; 3,087,936 ; 3,254,025 ; 3,282,955 ; 3,313,727 ; 3,491,025 ; 3,533,945 ; 3,666,662 and 4,925,983 .
  • Borated dispersant are prepared by reaction of one or more dispersant with one or more boron compounds.
  • the dispersants include acylated amines, carboxylic esters, Mannich reaction products, hydrocarbyl substituted.amines, ethoxylated amines, and mixtures thereof.
  • Acylated amines include reaction products of one or more carboxylic acylating agent and one or more amine.
  • the carboxylic acylating agents include C 8-30 fatty acids, C 14-20 isoaliphatic acids, C 18-44 dimer acids, addition dicarboxylic acids, trimer acids, addition tricarboxylic acids, and hydrocarbyl substituted carboxylic acylating agents.
  • the hydrocarbyl substituted carboxylic acylating agents are prepared by a reaction of an olefin or polyalkene with an unsaturated carboxylic reagent, such as maleic anhydride.
  • the amines may be any of those described above or a polyamine, such as an alkylenepolyamine or a condensed polyamine.
  • Carboxylic ester dispersants are prepared by reacting a carboxylic acylating agent with an organic hydroxy compound and optionally an amine. Suitable alcohols include polyhydric alcohols, such pentaerythritol. Carboxylic ester dispersant is described in U.S. Pat. Nos. 3,522,179 and 4,234,435
  • the dispersant may be a hydrocarbyl-substituted amine, such as are disclosed in U.S. Pat. Nos. 3,275,554 ; 3,438,757 ; 3,454,555 ; 3,565,804 ; 3,755,433 ; and 3,822,289 .
  • hydrocarbyl substituted amines are prepared by reacting olefins and olefin polymers, with amines (mono- or polyamines).
  • the amine may be, for example, an alkylenepolyamine.
  • the dispersant may be a Mannich dispersant.
  • Mannich dispersants are generally formed by the reaction of an aldehyde, such as formaldehyde or paraformaldehyde, an amine such as a polyamine (e.g., a polyalkylenepolyamine), and a substituted hydroxyaromatic compound.
  • the amounts of the reagents are typically in a mole ratio of hydroxyaromatic compound to formaldehyde to amine of (1:1:1) to (1:3:3).
  • the hydroxyaromatic compound is generally an alkyl substituted hydroxyaromatic compound.
  • Mannich dispersants are described in the following patents: U.S. Pat. No. 3,980,569 ; U.S. Pat. No. 3,877,899 ; and U.S. Pat. No. 4,454,059 .
  • the boron compound useful in the present invention can also be a reaction product of a dialkanolamine and boric acid, further reacted with a C 8 to C 20 fatty acid, that is to say, long chain alkenyl amide borates.
  • a reaction product of mixed fatty acids such as tall oil acids with diethanolamine and boric acid.
  • the boron compound can be the reaction product of a borating agent such as boric acid with a condensation product of a fatty acid (such as stearic acid or isostearic acid) with a polyamine such as tetraethylenepentamine.
  • a borating agent such as boric acid
  • a condensation product of a fatty acid such as stearic acid or isostearic acid
  • a polyamine such as tetraethylenepentamine.
  • condensation products are described, for instance, in U.S. Patent Application 2005 0014656 , and may be in the form of an amide, am imidazoline, or mixtures thereof.
  • the boron compound can be an alkali or mixed alkali metal and alkaline earth metal borate.
  • These metal borates can be hydrated particulate metal borates, which are available commercially and are known in the art from U.S. Patents. 3,997,454 ; 3,819,521 ; 3,853,772 ; 3,907,601 ; 3,997,454 ; and 4,089,790 .
  • the amount of the boron compound will typically be 0.05 to 2 weight percent. The desired amount will, naturally, depend to some extent on the particular boron compound and the amount of boron present in such compound. Typical amounts, for borated dispersants or other boron-containing materials, can also be 0.08 to 1 percent or 0.1 to 0.8 percent or 0.15 to 0.7 percent or 0.2 to 0.5 percent. Alternatively expressed, the amount of the boron compound is sufficient to provide 40 to 4000 parts per million by weight boron to the composition, or it can be 100 to 1000 or 200 to 800 parts per million.
  • the lubricating composition useful in the present invention will also contain at least one friction modifier. Since some of the above-described boron compounds can themselves function as friction modifiers, the present compositions will normally contain a friction modifier other than or in addition to a boron compound, such that any of the boron-containing materials will not be counted as one of the required friction modifiers. Friction modifiers are well known to those skilled in the art. A useful list of friction modifiers is included in U.S. Pat. No. 4,792,410 .
  • Suitable friction modifiers include: (i) fatty phosphites; (ii) fatty acid amides; (iii) fatty epoxides; (iv) fatty amines; (v) fatty esters (e.g, glycerol esters, that is, fatty acid glycerides); (vi) alkoxylated fatty amines; (vii) metal salts of fatty acids; (viii) sulfurized olefins; (ix) fatty imidazolines; (x) condensation products of carboxylic acids and polyalkylene-polyamines; (xi) metal salts of alkyl salicylates; (xii) amine salts of alkylphosphoric acids; and mixtures thereof.
  • fatty phosphites also referred to as fatty alkyl hydrogen phosphites
  • Dialkyl phosphite as shown in the preceding formula, is typically present with a minor amount of monoalkyl phosphite of the formula (RO)(HO)PHO.
  • R is conventionally referred to as an alkyl group. It is, of course, possible that the alkyl is actually alkenyl and thus the terms "alkyl” and “alkylated,” as used herein, will embrace other than saturated alkyl groups within the phosphite.
  • the phosphite will normally have sufficient hydrocarbyl groups of sufficient length to render the phosphite substantially oleophilic, e.g., 8 to 24 or 12 to 22 or 16 to 20 carbon atoms in each group.
  • the hydrocarbyl groups can be substantially unbranched.
  • Many suitable phosphites are available commercially and may be synthesized as described in U.S. Patent 4,752,416 .
  • the fatty phosphite can be formed from oleyl groups, thus having 18 carbon atoms in each fatty radical.
  • alkoxylated fatty amines and (iv) fatty amines themselves (such as oleylamine) are generally useful as friction modifiers in this invention.
  • Such amines are commercially available, as described above for borated fatty amines.
  • suitable amines are secondary or tertiary amine represented by the formula R 1 R 2 NR 3 where R 1 and R 2 are each independently an alkyl group of at least 6 carbon atoms and R 3 is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group.
  • Fatty acid esters such as those of glycerol (v) can be used as friction modifiers. These materials can be prepared by a variety of methods well known in the art. Many of these esters, such as glycerol monooleate and glycerol tallowate, are manufactured on a commercial scale. The esters useful are oil-soluble and can be prepared from C 8 to C 22 fatty acids or mixtures thereof such as are found in natural products and as are described in greater detail below. Fatty acid monoesters of glycerol are suitable, and mixtures of mono- and diesters may also be used. For example, commercial glycerol monooleate may contain a mixture of 45% to 55% by weight monoester and 55% to 45% diester. Other fatty esters, such as pentaerythritol monooleate or other partial esters of pentaerythritol or other polyols, are also contemplated.
  • Fatty acids can be used in preparing the above glycerol esters; they can also be used in preparing their (vii) metal salts, (ii) amides, and (ix) imidazolines, any of which can also be used as friction modifiers.
  • Suitable fatty acids include those containing 6 to 24 carbon atoms, e.g., 8 to 18. The acids can be branched or straight-chain, saturated or unsaturated.
  • Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, and linolenic acids, and the acids from the natural products tallow, palm oil, olive oil, peanut oil, corn oil, and Neat's foot oil.
  • a particularly preferred acid is oleic acid.
  • Suitable metal salts of such acids include zinc and calcium salts, although zinc salts may be avoided of a low zinc composition is desired. Examples are overbased calcium salts and basic oleic acid-zinc salt complexes which can be represented by the general formula Zn 4 Oleate 3 O 1 .
  • Suitable amides include those prepared by condensation with ammonia or with primary or secondary amines such as diethylamine and diethanolamine.
  • Fatty imidazolines (ix) are the cyclic condensation product of an acid with a diamine or polyamine such as a polyethylenepolyamine.
  • the imidazolines are generally represented by the structure where R is an alkyl group and R' is hydrogen or a hydrocarbyl group or a substituted hydrocarbyl group, including -(CH 2 CH 2 NH)n- groups.
  • the friction modifier can be the condensation product of a C 8 to C 24 fatty acid with a polyalkylene polyamine, and in particular, the product of isostearic acid with tetraethylenepentamine.
  • the condensation products of carboxylic acids and polyalkyleneamines (x) may generally be imidazolines or amides.
  • Sulfurized olefins (vii) are well known commercial materials used as friction modifiers. They may be prepared in accordance with the detailed teachings of U.S. Patents 4,957,651 and 4,959,168 . Described therein is a cosulfurized mixture of 2 or more reactants selected from the group consisting of (1) at least one fatty acid ester of a polyhydric alcohol, (2) at least one fatty acid, (3) at least one olefin, and (4) at least one fatty acid ester of a monohydric alcohol. Reactant (3), the olefin component, comprises at least one olefin.
  • This olefin can be an aliphatic olefin, which usually will contain 4 to 40 carbon atoms, or 8 to 36 carbon atoms. Terminal olefins, or alpha-olefins, are suitable, especially those having from 12 to 20 carbon atoms. Mixtures of these olefins are commercially available, and such mixtures may be used.
  • Metal salts of alkyl salicylates (xi) include calcium and other salts of long chain (e.g. C 12 to C 16 ) alkyl-substituted salicylic acids.
  • Amine salts of alkylphosphoric acids (xii) include salts of oleyl and other long chain esters of phosphoric acid, with amines as described herein.
  • Useful amines in this regard are tertiary-aliphatic primary amines, some of which are sold under the tradename PrimeneTM.
  • the amines are non-branched, since it is believed that amines with non-branched hydrocarbyl groups may provide superior friction performance.
  • the amount of the friction modifier is 0.2 to 2 percent by weight of the lubricating composition, preferably 0.3 to 2 or 0.5 to 1.5 percent.
  • Viscosity modifiers VM
  • dispersant viscosity modifiers DVM
  • examples of VMs and DVMs are polymethacrylates, polyacrylates, polyolefins, styrene-maleic ester copolymers, and similar polymeric substances including homopolymers, copolymers and graft copolymers.
  • VMs, DVMs and their chemical types include polyisobutylenes, olefin copolymers, hydrogenated styrene-diene copolymers, styrene/maleate copolymers, which are dispersant copolymers, polymethacrylates, some of which have dispersant properties, olefin-graft-polymethacrylate polymers, and hydrogenated polyisoprene star polymers.
  • Viscosity modifiers can be found in U.S. patents 5,157,088 , 5,256,752 and 5,395,539 .
  • the VMs and/or DVMs may be incorporated into the fully-formulated compositions, if desired, at a level of up to 15% by weight or greater, such as 1 to 12 % or 3 to 10 %.
  • antioxidants that is, oxidation inhibitors
  • hindered phenolic antioxidants e.g., di-t-butylphenol
  • secondary aromatic amine antioxidants e.g., mono- and/or dinonyl diphenylamines
  • sulfurized phenolic antioxidants oil-soluble copper compounds, phosphorus-containing antioxidants
  • organic sulfides, disulfides, and polysulfides include seal swell compositions, such as isodecyl sulfolane or phthalate esters, which are designed to keep seals pliable.
  • pour point depressants such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers.
  • pour point depressants such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers.
  • These optional materials are known to those skilled in the art, are generally commercially available, and are described in greater detail in published European Patent Application 761,805 .
  • corrosion inhibitors such as acids and anhydrides (e.g., polyisobutene succinic acid or anhydride), dyes, fluidizing agents, odor masking agents, and antifoam agents.
  • the formulations useful in the present invention permit the successful lubrication of mechanical devices such as farm tractors without the necessity of using such zinc salts as zinc dialkyldithiophosphates (ZDPs). While ZDPs normally provide antioxidancy, anti-corrosion activity, antiwear activity and other benefits, the compositions of the present invention are typically substantially free from ZDPs. By “substantially free from ZDP” it is meant that the formulation is prepared without the intentional addition of any ZDP, or alternatively, only a very small amount of ZDP, i.e. the formulation contains less than 0.5 percent by weight ZDP. The formulation may contain 0.005 to 0.3 percent or 0.01 to 0.1 or 0.001 to 0.05 percent or less of ZDPs.
  • the formulations are substantially free from zinc compounds of any type, thus containing, e.g., less than 0.05 percent by weight Zn or 0.0005 to 0.03 percent or 0.001 to 0.01 or 0.0001 to 0.005 percent or less of Zn.
  • the ZDPs (which are present in only a low amount or are substantially absent) may be represented by the formula
  • the R 8 and R 9 groups are hydrocarbyl groups typically alkyl, cycloalkyl, aralkyl or alkaryl group having 3 to 20 carbon atoms, such as 3 to 16 carbon atoms or up to 13 carbon atoms, e.g., 3 to 12 carbon atoms.
  • the alcohols which are used to provide the R 8 and R 9 groups can be one or more primary alcohols, one or more secondary alcohols, or a mixture of secondary alcohol and primary alcohol. A mixture of two secondary alcohols such as isopropanol and 4-methyl-2-pentanol are often used in preparing ZDPs.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • Lubricant compositions are prepared from the components listed in the following Tables: Table 1
  • Example 1 Component Amount, % Borated succinimide dispersant, including 33% oil, 1.9% B (boron source) 0.5 Dispersant/corrosion inhibitor comprising DMTD reacted with an ester dispersant, containing about 10% DMTD, 49% oil 1.0 C 12-14 alkyl amine salt of mono and diesters of phosphoric acid (extreme pressure agent) 0.4 Glycerol monooleate (commercial grade) (friction modifier) 0.5 Oleamide (friction modifier) 0.35 Tall oil acid, product with diethanolamine and boric acid (antiwear agent, boron source) 0.2 Dibutyl hydrogen phosphite (anti-wear agent) 0.25 Di-t-butyl phenol (antioxidant) 0.2 Calcium alklbenzenesulfonate detergent, including 42% oil, 400 TBN (detergent) 0.8 Oil of lubricating viscosity balance Table 2 Component
  • the JDQ-84 dynamic corrosion test evaluates whether oils, when contaminated with limited amounts of water, can still serve as suitable fluids for pumps found on agricultural equipment. After running the test oil through an axial piston pump at 82°C, 34.5 MPa, 1.5 L/sec, for 25 hours, 1% water is added to the oil and the test continued for an additional 200 hours. Reduction in flow, if any, is reported, as well as the presence of Cu and Fe in the drain fluid. The samples tested pass this test.
  • the JDQ-95 test measures a fluid's antiwear capability as measured in tractor spiral bevel and final drive gear sets.
  • a modified front drive axle assembly is used as the test device.
  • the test is conducted using new spiral bevel ring gear and pinions, final drive sun pinions, and associated planet pinion gears. After 74 hours total testing with the test fluid, the unit is drained and the North and South sun pinion gear teeth are measured for wear, reported in ⁇ m (originally measured as micro-inches) and a visual rating on a scale of 1 - 10 is assigned.
  • a spiral bevel rating of 7 or higher is considered a passing result.
  • the "average rating" is determined from a total of 6 distress merit ratings on both the ring gear and drive pinion. The samples examined pass this test.
  • the JDQ-96 test assesses the effect of test oil on brake noise and brake capacity compared to that of a reference oil.
  • the test is run at 10,000, 20,000, and 30,000 cycles. Results are presented as torque (arbitrary units, in thousands) as well as variation in torque, that is, variability, in the same units, which is a measure of "chatter.”
  • a reference material exhibits a value of 333,913 at 30,000 cycles with a variation of 69,178.
  • the samples tested provide very strong passing values.
  • lubricant as described herein may be principally used for lubricating the hydraulic system of a farm tractor, it may also be used for lubricating other mechanical devices such as gears, gear boxes, transmissions for automobiles and other vehicles, including manual transmissions, automatic transmissions, continuously variable transmissions, traction drives, dual clutch transmissions, and transmissions for hybrid (e.g., gasoline and electric) vehicles, as well as other devices such as wind turbines and other machinery.
  • the composition may be used as, or as a part of, a grease or a non-grease lubricant.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated.
  • the upper and lower amount, range, and ratio limits set forth herein may be independently combined.
  • the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.
  • the expression "consisting essentially of" permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

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Claims (9)

  1. Verfahren zum Schmieren des Hydrauliksystems eines Ackerschleppers, bei dem man dieses mit einer Schmiermittelzusammensetzung versorgt, die Folgendes umfasst:
    (a) ein Öl mit Schmierviskosität mit einer kinematischen Viskosität bei 100°C von bis zu 10 mm2/s;
    (b) mindestens ein Aminsalz eines Phosphorsäureesters, wobei die Menge des Aminsalzes 0,04 bis 4 Gewichtsprozent beträgt;
    (c) mindestens eine Thiadiazolverbindung, wobei die Menge der Thiadiazolverbindung 0,01 bis 5 Gewichtsprozent beträgt;
    (d) mindestens ein überalkalisiertes Calciumsulfonatdetergens, wobei die Menge des überalkalisierten Calciumsulfonatdetergens 0,05 bis 6 Gewichtsprozent beträgt;
    (e) mindestens eine Borverbindung, bei der es sich nicht um ein überalkalisiertes Metalldetergens handelt, wobei die Menge der Komponente (e) zur Bereitstellung von 40 bis 4000 ppm B an die Zusammensetzung ausreicht;
    (f) mindestens einen Reibungsmodifikator, bei dem es sich nicht um eine Borverbindung handelt, wobei die Menge des Reibungsmodifikators 0,2 bis 2 Gewichtsprozent der Schmiermittelzusammensetzung beträgt;
    wobei die Zusammensetzung weniger als 0,5 Gewichtsprozent Zinkdialkyldithiophosphat enthält.
  2. Verfahren nach Anspruch 1, bei dem das Aminsalz von (b) ein C8- bis C20-Alkylaminsalz eines Mono- oder Dialkylphosphatesters oder Mischungen davon umfasst.
  3. Verfahren nach Anspruch 1, bei dem die Thiadiazolverbindung von (c) aus der Gruppe bestehend aus 2-Alkyldithio-5-mercapto-[1,3,4]-thiadiazolen, 2,5-Bis(alkyldithio)-[1,3,4]-thiadiazolen, 2-Alkylhydroxyphenylmethylthio-5-mercapto-[1,3,4]-thiadiazolen und Mischungen davon ausgewählt ist.
  4. Verfahren nach Anspruch 1, bei dem die Thiadiazolverbindung von (c) das Umsetzungsprodukt von 2,5-Dimercapto-[1,3,4]-thiadiazol mit einem stickstoffhaltigen Dispergiermittel umfasst.
  5. Verfahren nach Anspruch 1, bei dem die Borverbindung von Komponente (e) das Umsetzungsprodukt von einem Dialkanolamin und Borsäure, weiter umgesetzt mit einer C8- bis C20-Fettsäure, umfasst.
  6. Verfahren nach Anspruch 1, bei dem Komponente (e) ein boriertes stickstoffhaltiges Dispergiermittel oder ein boriertes ethoxyliertes Amin umfasst.
  7. Verfahren nach Anspruch 1, bei dem der Reibungsmodifikator (f) aus der Gruppe bestehend aus Fettsäureamiden, Fettsäureestern, Metallsalzen von Fettsäuren, Fettimidazolinen und Mischungen davon ausgewählt ist.
  8. Verfahren nach Anspruch 1, ferner umfassend mindestens ein zusätzliches Additiv aus der Gruppe bestehend aus Viskositätsmodifikatoren, Pourpoint-Erniedrigern, Antioxidantien, Rostschutzmitteln, Dichtungsquellungszusammensetzungen und Antischaummitteln.
  9. Verfahren nach Anspruch 1, bei dem die Schmiermittelzusammensetzung durch Mischen der Komponenten von Anspruch 1 hergestellt wird.
EP06785653.4A 2005-06-29 2006-06-27 Zinkfreies ackerschlepperfluid Revoked EP1910505B1 (de)

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Also Published As

Publication number Publication date
EP1910505A2 (de) 2008-04-16
BRPI0611715B1 (pt) 2016-03-15
CA2613438A1 (en) 2007-01-11
BRPI0611715A2 (pt) 2010-09-28
CA2613438C (en) 2014-03-25
AU2006266095B2 (en) 2010-08-05
US20090215657A1 (en) 2009-08-27
WO2007005423A2 (en) 2007-01-11
WO2007005423A3 (en) 2007-03-01
AU2006266095A1 (en) 2007-01-11

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