US20050202979A1 - Power transmission fluids with enhanced extreme pressure characteristics - Google Patents

Power transmission fluids with enhanced extreme pressure characteristics Download PDF

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Publication number
US20050202979A1
US20050202979A1 US11/075,569 US7556905A US2005202979A1 US 20050202979 A1 US20050202979 A1 US 20050202979A1 US 7556905 A US7556905 A US 7556905A US 2005202979 A1 US2005202979 A1 US 2005202979A1
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Prior art keywords
oil
phenate
amine
acid
ester
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US11/075,569
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Timothy Henly
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Afton Chemical Corp
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Afton Chemical Corp
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Priority to US11/075,569 priority Critical patent/US20050202979A1/en
Assigned to ETHYL PETROLEUM ADDITIVES, INC. reassignment ETHYL PETROLEUM ADDITIVES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HENLY, TIMOTHY J.
Publication of US20050202979A1 publication Critical patent/US20050202979A1/en
Assigned to SUNTRUST BANK reassignment SUNTRUST BANK SECURITY AGREEMENT Assignors: AFTON CHEMICAL CORPORATION
Assigned to AFTON CHEMICAL CORPORATION reassignment AFTON CHEMICAL CORPORATION RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: SUNTRUST BANK
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/12Chemical after-treatment of the constituents of the lubricating composition by phosphorus or a compound containing phosphorus, e.g. PxSy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present disclosure relates to power transmission fluids having improved characteristics particularly for extreme pressure applications.
  • the power transmission fluids disclosed herein may include fluids suitable for use in an automatic transmission (ATF) and/or a manual transmission.
  • Extremely high metal-on-metal pressures are present in newer automatic and manual transmissions such as step automatic transmissions, continuously variable transmissions, manual or automated manual transmissions.
  • High pressures are also present in various gear drive components such as automotive differentials and power transmission gear drive components.
  • the high pressures present in such transmission and gear drive components mean that lubricants used in these systems must be suitable for such extreme pressure applications to prevent wear and avoid seizure of the rotating and contacting components.
  • lubricants used in these systems must be suitable for such extreme pressure applications to prevent wear and avoid seizure of the rotating and contacting components.
  • Power transmission fluids formulated according to the present disclosure provide improved high pressure characteristics.
  • additives and fluids containing the additives are described which are suitably formulated to protect transmission and drive components in metal-on-metal contact situations.
  • a power transmission fluid composition for extreme pressure applications includes a base oil, and an additive composition containing an extreme pressure performance improving amount of an ester of phosphonic acid of the formula: where R 1 is a hydrocarbyl group containing from about 8 to about 24 carbon atoms, R 2 and R 3 are independently selected from hydrogen and a hydrocarbyl group containing from about 1 to about 8 carbon atoms, provided that no more than one of R 2 and R 3 is hydrogen.
  • the additive also includes a succinimide dispersant, and, optionally, a metal-based detergent. When used, the detergent component is substantially devoid of calcium cations.
  • Another embodiment provides a method of improving extreme pressure characteristics for a transmission fluid.
  • the method includes providing a base oil and adding to the base oil an additive composition comprising (1) from about 0.01 to about 1.0 weight percent based on the total weight of the base oil and additive composition of an ester of phosphonic acid of the formula:
  • R 1 is a hydrocarbyl group containing from about 8 to about 24 carbon atoms
  • R 2 and R 3 are independently selected from hydrogen and a hydrocarbyl group containing from about 1 to about 8 carbon atoms, provided that no more than one of R 2 and R 3 is hydrogen.
  • the additive composition also includes from about 2 to about 5 weight percent based on the total weight of the transmission fluid of a succinimide dispersant and, optionally, from about 0.0 to about 0.2 weight percent based on the total weight of the transmission fluid of a metal-based detergent.
  • the detergent is substantially devoid of calcium cations.
  • the additive concentrate includes a base oil carrier fluid.
  • Another component of the additive concentrate is an extreme pressure performance improving amount of an ester of phosphonic acid of the formula: where R 1 is a hydrocarbyl group containing from about 8 to about 24 carbon atoms, R 2 and R 3 are independently selected from hydrogen and a hydrocarbyl group containing from about 1 to about 8 carbon atoms, provided that no more than one of R 2 and R 3 is hydrogen.
  • a succinimide dispersant and an optional metal-based detergent may also be included in the additive concentrate.
  • the detergent is substantially devoid of calcium cations.
  • Power transmission fluids of the foregoing embodiments are formulated to provide enhanced extreme pressure properties for applications where metal-to-metal contact is made under high pressures, e.g., pressures in excess of 2 GPa.
  • Such fluids are suitable for automatic and manual transmissions such as step automatic transmissions, continuously variable transmissions, manual or automated manual transmissions.
  • High metal-to-metal contact pressures such as those found in automotive transmissions, for example, may cause damage to transmission parts if a lubricant is used that does not possess sufficient extreme pressure protection characteristics.
  • power transmission fluid compositions as described herein have greatly improved extreme pressure performance characteristics.
  • 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 a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
  • the oils used to lubricate those transmissions may be formulated to endure higher temperatures and pressures.
  • the oil additive packages may be formulated so that important oil properties change as little as possible in the face of these stresses.
  • An important characteristic of a power transmission fluid is its extreme pressure properties. High metal-on-metal contact pressures found in newer automotive transmissions and in gear drives can cause damage to transmission parts and gear drives if the lubricant used in the system is not formulated to provide sufficient extreme pressure protective properties.
  • a power transmission fluid may include a base oil and an additive composition.
  • the additive composition includes an extreme pressure performance improving amount of an ester of phosphonic acid of the formula: where R 1 is a hydrocarbyl group containing from about 8 to about 24 carbon atoms, R 2 and R 3 are independently selected from hydrogen and a hydrocarbyl group containing from about 1 to about 8 carbon atoms, provided that no more than one of R 2 and R 3 is hydrogen.
  • the additive also includes a succinimide dispersant, and, optionally, a metal-based detergent. When used, the detergent is substantially devoid of calcium cations.
  • the succinimide dispersant used in such fluids may be a post-treated succinimide dispersant.
  • the phosphonic acid ester may be a di-organo or tri-organo phosphonate.
  • Examples include, but are not limited to, methyloctadecylhydrogen phosphonate, bis(2-ethylhexyl)2-ethylhexyl phosphonate, ethyloctadecylhydrogen phosphonate, dimethyloctadecylphosphonate, dimethylocta-decenylphosphonate, diethyl-2-ethyldecylphosphonate, ethylpropyl-1-butylhexadecyl-phosphonate, methylethyloctadecylphosphonate, methylbutyl eicosyl-phosphonate, dimethylhexatriacontylphosphonate.
  • Methods for making phosphonic acid esters are described in U.S. Pat. No. 2,2724,718 to Siles et al.,
  • An extreme pressure performance improving amount of the ester of phosphonic acid as described above in combination with a base oil to provide a power transmission fluid may range from about 0.01 to about 1.0 percent by weight of the total weight of the transmission fluid, as a further example, from about 0.03 to about 0.5 weight percent, and as an even further example, from about 0.03 to about 0.25 weight percent.
  • Base oils suitable for use in formulating transmission fluid compositions according to the invention may be selected from any of the synthetic or natural oils or mixtures thereof.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) 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. Oils derived from coal or shale are also suitable.
  • the base oil typically has a viscosity of, for example, from about 2 to about 15 cSt and, as a further example, from about 2 to about 10 cSt at 100° C. Further, oils derived from a gas-to-liquid process are also suitable.
  • Synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, etc.); polyalphaolefins such as poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, etc.); polyalphaolefins such as poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc.
  • alkylbenzenes e.g., dodecylbenzenes, tetradecylbenzenes, di-nonylbenzenes, di-(2-ethylhexyl)benzenes, etc.
  • polyphenyls e.g., biphenyls, terphenyl, alkylated polyphenyls, etc.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic oils that may be used.
  • Such oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3-8 fatty acid esters, or the C 13 Oxo acid diester of tetraethylene glycol.
  • esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.
  • alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.
  • these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecy
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
  • the base oil used which may be used to make the transmission fluid compositions as described herein may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • Such base oil groups are as follows: Base Oil Group 1 Sulfur (wt. %) Saturates (wt. %) Viscosity Index Group I >0.03 and/or ⁇ 90 80 to 120 Group II ⁇ 0.03 And ⁇ 90 80 to 120 Group II ⁇ 0.03 And ⁇ 90 ⁇ 120 Group IV all polyalphaolefins (PAOs) Group V all others not included in Groups I-IV 1 Groups I-III are mineral oil base stocks.
  • PAOs polyalphaolefins
  • the base oil may be a poly-alpha-olefin (PAO).
  • PAO poly-alpha-olefin
  • the poly-alpha-olefins are derived from monomers having from about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms.
  • useful PAOs include those derived from octene, decene, mixtures thereof, and the like.
  • PAOs may have a viscosity of from about 2 to about 15, or from about 3 to about 12, or from about 4 to about 8 cSt at 100° C.
  • PAOs include 4 cSt at 100° C. poly-alpha-olefins, 6 cSt at 100° C. poly-alpha-olefins, and mixtures thereof. Mixtures of mineral oil with the foregoing poly-alpha-olefins may be used.
  • the base oil may be an oil derived from Fischer-Tropsch synthesized hydrocarbons.
  • Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst.
  • Such hydrocarbons typically require further processing in order to be useful as the base oil.
  • the hydrocarbons may be hydroisomerized using processes disclosed in U.S. Pat. No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using processes disclosed in U.S. Pat. No. 4,943,672 or 6,096,940; dewaxed using processes disclosed in U.S. Pat. No. 5,882,505; or hydroisomerized and dewaxed using processes disclosed in U.S. Pat. No. 6,013,171; 6,080,301; or 6,165,949.
  • Unrefined, refined and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the base oils.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives, contaminants, and oil breakdown products.
  • the ashless dispersant used in the transmission fluids as described herein may be selected from any of the ashless dispersants known to those skilled in the art. Suitable ashless dispersants may include ashless dispersants such as succinimide dispersants, Mannich base dispersants, and polymeric polyamine dispersants. Hydrocarbyl-substituted succinic acylating agents are used to make hydrocarbyl-substituted succinimides.
  • the hydrocarbyl-substituted succinic acylating agents include, but are not limited to, hydrocarbyl-substituted succinic acids, hydrocarbyl-substituted succinic anhydrides, the hydrocarbyl-substituted succinic acid halides (especially the acid fluorides and acid chlorides), and the esters of the hydrocarbyl-substituted succinic acids and lower alcohols (e.g., those containing up to 7 carbon atoms), that is, hydrocarbyl-substituted compounds which can function as carboxylic acylating agents.
  • Hydrocarbyl substituted acylating agents are made as by reacting a polyolefin or chlorinated polyolefin of appropriate molecular weight with maleic anhydride. Similar carboxylic reactants can be used to make the acylating agents. Such reactants may include, but are not limited to, maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid, and the like, including the corresponding acid halides and lower aliphatic esters.
  • the molecular weight of the olefin can vary depending upon the intended use of the substituted succinic anhydrides.
  • the substituted succinic anhydrides will have a hydrocarbyl group of from 8-500 carbon atoms.
  • substituted succinic anhydrides used to make lubricating oil dispersants will typically have a hydrocarbyl group of about 40-500 carbon atoms.
  • the olefins used to make these substituted succinic anhydrides may include a mixture of different molecular weight components resulting from the polymerization of low molecular weight olefin monomers such as ethylene, propylene and isobutylene.
  • the mole ratio of maleic anhydride to olefin can vary widely. It may vary, for example, from about 5:1 to about 1:5, or for example, from about 1:1 to about 3:1. With olefins such as polyisobutylene having a number average molecular weight of about 500 to about 7000, or as a further example, about 800 to about 3000 or higher and the ethylene-alpha-olefin copolymers, the maleic anhydride may be used in stoichiometric excess, e.g. 1.1 to 3 moles maleic anhydride per mole of olefin. The unreacted maleic anhydride can be vaporized from the resultant reaction mixture.
  • olefins such as polyisobutylene having a number average molecular weight of about 500 to about 7000, or as a further example, about 800 to about 3000 or higher and the ethylene-alpha-olefin copolymers
  • the maleic anhydride may be used in
  • the ashless dispersant may include one or more alkenyl succinimides of an amine having at least one primary amino group capable of forming an imide group.
  • the alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with an amine containing at least one primary amino group.
  • the alkenyl succinic anhydride may be made readily by heating a mixture of polyolefin and maleic anhydride to about 180°-220° C.
  • the polyolefin may be a polymer or copolymer of a lower monoolefin such as ethylene, propylene, isobutene and the like, having a number average molecular weight in the range of about 300 to about 3000 as determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Amines which may be employed in forming the ashless dispersant include any that have at least one primary amino group which can react to form an imide group and at least one additional primary or secondary amino group and/or at least one hydroxyl group.
  • a few representative examples are: N-methyl-propanediamine, N-dodecylpropanediamine, N-aminopropyl-piperazine, ethanolamine, N-ethanol-ethylenediamine, and the like.
  • the ashless dispersant may include the products of the reaction of a polyethylene polyamine, e.g. triethylene tetramine or tetraethylene pentamine, with a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, such as polyisobutene, of suitable molecular weight, with an unsaturated polycarboxylic acid or anhydride, e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures of two or more such substances.
  • a polyethylene polyamine e.g. triethylene tetramine or tetraethylene pentamine
  • a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, such as polyisobutene, of suitable molecular weight
  • an unsaturated polycarboxylic acid or anhydride e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures
  • Additional polyamines useful in forming the hydrocarbyl-substituted succinimides include polyamines having at least one primary or secondary amino group and at least one tertiary amino group in the molecule as taught in U.S. Pat. Nos. 5,634,951 and 5,725,612.
  • suitable polyamines include N,N,N′′,N′′-tetraalkyldialkylenetriamines (two terminal tertiary amino groups and one central secondary amino group), N,N,N′,N′′-tetraalkyltrialkylenetetramines (one terminal tertiary amino group, two internal tertiary amino groups and one terminal primary amino group), N,N,N′,N′′,N′′′-pentaalkyltrialkylenetetramines (one terminal tertiary amino group, two internal tertiary amino groups and one terminal secondary amino group), tris(dialkylaminoalkyl)aminoalkylmethanes (three terminal tertiary amino groups and one terminal primary amino group), and like compounds, wherein the alkyl groups are the same or different and typically contain no more than about 12 carbon atoms each, and which may contain from 1 to 4 carbon atoms each. As a further example, these alkyl groups may be methyl and/or
  • the mole ratio of amine to hydrocarbyl-substituted succinic acid or anhydride may range from 1:1 to about 3.0:1.
  • Another example of a mole ratio of amine to hydrocarbyl-substituted succinic acid or anhydride may range from about 1.5:1 to about 2.0:1.
  • the foregoing dispersant may also be a post-treated dispersant made, for example, by treating the dispersant with maleic anhydride and boric acid as described, for example, in U.S. Pat. No. 5,789,353 to Scattergood, or by treating the dispersant with nonylphenol, formaldehyde and glycolic acid as described, for example, in U.S. Pat. No. 5,137,980 to DeGonia, et al.
  • the Mannich base dispersants may be a reaction product of an alkyl phenol, typically having a long chain alkyl substituent on the ring, with one or more aliphatic aldehydes containing from 1 to about 7 carbon atoms (especially formaldehyde and derivatives thereof), and polyamines (especially polyalkylene polyamines).
  • a Mannich base ashless dispersants may be formed by condensing about one molar proportion of long chain hydrocarbon-substituted phenol with from about 1 to about 2.5 moles of formaldehyde and from about 0.5 to about 2 moles of polyalkylene polyamine.
  • Polymeric polyamines may include hydrocarbyl polyamines wherein the hydrocarbyl group is composed of the polymerization product of isobutene and a raffinate I stream as described above.
  • PIB-amine and PIB-polyamines may also be used.
  • Borated dispersants may be formed by boronating (borating) an ashless dispersant having basic nitrogen and/or at least one hydroxyl group in the molecule, such as a succinimide dispersant, succinamide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, or hydrocarbyl amine or polyamine dispersant.
  • succinimide dispersant such as a succinimide dispersant, succinamide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, or hydrocarbyl amine or polyamine dispersant.
  • the borated dispersant may include a high molecular weight dispersant treated with boron such that the borated dispersant includes up to 2 wt % of boron.
  • the borated dispersant may include from about 0.8 wt % or less of boron.
  • the borated dispersant may include from about 0.1 to about 0.7 wt % of boron.
  • the borated dispersant may include from about 0.25 to about 0.7 wt % of boron.
  • the borated dispersant may include from about 0.35 to about 0.7 wt % of boron.
  • the dispersant may be dissolved in oil of suitable viscosity for ease of handling. It should be understood that the weight percentages given here are for neat dispersant, without any diluent oil added.
  • a dispersant may be present in the power transmission fluid in an amount of about 0.1 wt % to about 10 wt %. Further, the power transmission fluid may include from about 2 wt % to about 7 wt % of the borated dispersant. Further, the power transmission fluid may include from about 3 wt % to about 5 wt % of the borated dispersant. Further, the power transmission fluid may include an amount of the borated dispersant sufficient to provide up to 1900 parts per million (ppm) by weight of boron in the finished fluid, such as for example, from about 50 to about 500 ppm by weight of boron in the finished fluid.
  • ppm parts per million
  • Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkyl phenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octanol, Cellosolve.RTM. alcohol, Carbitol.RTM. alcohol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylene diamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine.
  • a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60° C. to 200° C.
  • overbased metal detergents are generally regarded as containing overbasing quantities of inorganic bases, generally in the form of micro dispersions or colloidal suspensions.
  • oil-soluble as applied to metallic detergents is intended to include metal detergents wherein inorganic bases are present that are not necessarily completely or truly oil-soluble in the strict sense of the term, inasmuch as such detergents when mixed into base oils behave much the same way as if they were fully and totally dissolved in the oil.
  • the various metallic detergents referred to herein above are sometimes called neutral, basic, or overbased alkali metal or alkaline earth metal-containing organic acid salts.
  • the metallic detergents utilized in this invention can, if desired, be oil-soluble boronated neutral and/or overbased alkali of alkaline earth metal-containing detergents.
  • Methods for preparing boronated metallic detergents are described in, for example, U.S. Pat. Nos. 3,480,548; 3,679,584; 3,829,381; 3,909,691; 4,965,003; and 4,965,004.
  • the power transmission fluid may also include conventional additives of the type used in automatic transmission fluid formulations and gear lubricants in addition to the extreme pressure performance improving additives described above.
  • additives include, but are not limited to, friction modifiers, antioxidants, viscosity index improvers, corrosion inhibitors, antirust additives, antiwear additives, metal deactivators, antifoamants, pour point depressants, air entrainment additives and/or seal swell agents.
  • the antiwear agents may include phosphorus-containing antiwear agents which may include an organic ester of phosphoric acid, phosphorous acid, or an amine salt thereof.
  • the phosphorus-containing antiwear agent may include one or more of a dihydrocarbyl phosphite, a trihydrocarbyl phosphite, a dihydrocarbyl phosphate, a trihydrocarbyl phosphate, any sulfur analogs thereof, and any amine salts thereof.
  • the phosphorus-containing antiwear agent may include at least one of dibutyl hydrogen phosphite (such as HiTEC® 528 antiwear agent available from Ethyl Corporation) and an amine salt of sulfurized dibutyl hydrogen phosphite (such as HiTEC® 833 antiwear agent available from Ethyl Corporation).
  • dibutyl hydrogen phosphite such as HiTEC® 528 antiwear agent available from Ethyl Corporation
  • an amine salt of sulfurized dibutyl hydrogen phosphite such as HiTEC® 833 antiwear agent available from Ethyl Corporation
  • the phosphorus-containing antiwear agent may be present in an amount sufficient to provide about 50 to about 500 parts per million by weight of phosphorus in the power transmission fluid.
  • the phosphorus-containing antiwear agent may be present in an amount sufficient to provide about 150 to about 300 parts per million by weight of phosphorus in the power transmission fluid.
  • the power transmission fluid may include from about 0.01 wt % to about 1.0 wt % of the phosphorus-containing antiwear agent. As a further example, the power transmission fluid may include from about 0.2 wt % to about 0.3 wt % of the phosphorus-containing antiwear agent. As an example, the power transmission fluid may include from about 0.1 wt % to about 0.2 wt % of a dibutyl hydrogen phosphite or 0.3 wt % to about 0.4 wt % an amine salt of a sulfurized dibutyl hydrogen phosphate.
  • Friction modifiers are used in automatic transmission fluids to decrease friction between surfaces (e.g., the members of a torque converter clutch or a shifting clutch) at low sliding speeds.
  • surfaces e.g., the members of a torque converter clutch or a shifting clutch
  • the result is a friction-vs.-velocity ( ⁇ -v) curve that has a positive slope, which in turn leads to smooth clutch engagements and minimizes “stick-slip” behavior (e.g., shudder, noise, and harsh shifts).
  • Friction modifiers include such compounds as aliphatic amines or ethoxylated aliphatic amines, ether amines, alkoxylated ether amines, aliphatic fatty acid amides, acylated amines, aliphatic carboxylic acids, aliphatic carboxylic esters, polyol esters, aliphatic carboxylic ester-amides, imidazolines, tertiary amines, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains one or more carbon atoms so as to render the compound suitably oil soluble.
  • the aliphatic group may contain about 8 or more carbon atoms.
  • aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia or primary amines.
  • the succinimide may include the reaction product of a succinic anhydride and ammonia or primary amine.
  • the alkenyl group of the alkenyl succinic acid may be a short chain alkenyl group, for example, the alkenyl group may include from about 12 to about 36 carbon atoms.
  • the succinimide may include a C 12 to about C 36 aliphatic hydrocarbyl succinimide.
  • the succinimide may include a C 16 to about C 28 aliphatic hydrocarbyl succinimide.
  • the succinimide may include a C 18 to about C 24 aliphatic hydrocarbyl succinimide.
  • the succinimide may be prepared from a succinic anhydride and ammonia as described in European Patent Application No. 0 020 037, herein incorporated by reference. Further, the succinimide may include HiTEC® 3191 friction modifier, available from Ethyl Corporation. In some embodiments, no non-metallic friction modifier other than the succinimide disclosed herein is included.
  • the succinimide may include one or more of a compound having the following structure:
  • One group of friction modifiers includes the N-aliphatic hydrocarbyl-substituted diethanol amines in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms.
  • An example of a suitable friction modifier system is composed of a combination of at least one N-aliphatic hydrocarbyl-substituted diethanol amine and at least one N-aliphatic hydrocarbyl-substituted trimethylene diamine in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms. Further details concerning this friction modifier system are set forth in U.S. Pat. Nos. 5,372,735 and 5,441,656.
  • Another friction modifier system is based on the combination of (i) at least one di(hydroxyalkyl) aliphatic tertiary amine in which the hydroxyalkyl groups, being the same or different, each contain from 2 to about 4 carbon atoms, and in which the aliphatic group is an acyclic hydrocarbyl group containing from about 10 to about 25 carbon atoms, and (ii) at least one hydroxyalkyl aliphatic imidazoline in which the hydroxyalkyl group contains from 2 to about 4 carbon atoms, and in which the aliphatic group is an acyclic hydrocarbyl group containing from about 10 to about 25 carbon atoms.
  • GMO glycerol monooleate
  • GML glycerol monolaurate
  • compositions may contain up to about 1.25 wt %, or, as a further example, from about 0.05 to about 1 wt % of one or more friction modifiers.
  • antioxidant compounds may be included in the compositions.
  • Antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfurized phenolic antioxidants, and organic phosphites, among others.
  • phenolic antioxidants include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4′-methylenebis(2,6-di-tert-butylphenol),2,2′-methylenebis(4-methyl-6-ter t-butylphenol), mixed methylene-bridged polyalkyl phenols, and 4,4′-thiobis(2-methyl-6-tert-butylphenol).
  • antioxidant in the transmission fluid compositions described herein may range from about 0.01 to about 3.0 wt % based on the total weight of the fluid formulation. As a further example, antioxidant may be present in an amount from about 0.1 wt % to about 1.0 wt %.
  • copper corrosion inhibitors may constitute another class of additives suitable for inclusion in the compositions.
  • Such compounds include thiazoles, triazoles and thiadiazoles.
  • examples of such compounds include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercapto benzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles.
  • Suitable compounds include the 1,3,4-thiadiazoles, a number of which are available as articles of commerce, and also combinations of triazoles such as tolyltriazole with a 1,3,5-thiadiazole such as a 2,5-bis(alkyldithio)-1,3,4-thiadiazole.
  • Materials of these types that are available on the open market include COBRATEC TT-100 and HiTEC® 4313 additive (Ethyl Corporation).
  • the 1,3,4-thiadiazoles are generally synthesized from hydrazine and carbon disulfide by known procedures. See, for example, U.S. Pat. Nos. 2,765,289; 2,749,311; 2,760,933; 2,850,453; 2,910,439; 3,663,561; 3,862,798; and 3,840,549.
  • Rust or corrosion inhibitors are another type of inhibitor additive for use in embodiments of the present disclosure.
  • Such materials include monocarboxylic acids and polycarboxylic acids.
  • suitable monocarboxylic acids are octanoic acid, decanoic acid and dodecanoic acid.
  • Suitable polycarboxylic acids include dimer and trimer acids such as are produced from such acids as tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humko Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Henkel Corporation.
  • rust inhibitor may comprise alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like.
  • alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like
  • Suitable rust or corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; aminosuccinic acids or derivatives thereof, and the like. Materials of these types are available as articles of commerce. Mixtures of such rust or corrosion inhibitors can be used.
  • the amount of corrosion inhibitor in the transmission fluid formulations described herein may range from about 0.01 to about 2.0 wt % based on the total weight of the formulation.
  • Viscosity index improvers for use in the above described fluid transmission and gear lubricant compositions may be selected from polyisoalkylene compounds, polymethacrylate compounds, and any conventional viscosity index improvers.
  • An example of a suitable polyisoalkylene compound for use as a viscosity index improver includes polyisobutylene having a weight average molecular weight ranging from about 700 to about 2,500.
  • Embodiments may include a mixture of one or more viscosity index improvers of the same or different molecular weight.
  • Suitable commercially available viscosity index improvers may include styrene-maleic esters such as are available under the trade designation LUBRIZOL® 3702, LUBRIZOL® 3706 and LUBRIZOL® 3715 available from The Lubrizol Corporation; polyalkylmethacrylates such as those available from ROHM GmbH (Darmstadt, Germany) under the trade designations: VISCOPLEX® 5543, VISCOPLEX® 5548, VISCOPLEX® 5549, VISCOPLEX® 5550, VISCOPLEX® 5551 and VISCOPLEX® 5151, from Rohm & Haas Company (Philadelphia, Pa.) under the trade designations ACRYLOID® 1277, ACRYLOID® 1265 and ACRYLOID® 1269, and from Ethyl Corporation (Richmond, Va.) under the trade designation HiTEC® 5710, HiTEC® 5738, HiTEC® 5739, and HiTEC® 5742; and olefin copolymer viscosity
  • a foam inhibitor may form another component suitable for use in the compositions.
  • Foam inhibitors may be selected from silicones, polyacrylates, surfactants, and the like.
  • One suitable acrylic defoamer material is PC-1244 available from Monsanto Company.
  • the amount of antifoam agent in the transmission fluid formulations described herein may range from about 0.01 wt % to about 0.5 wt % based on the total weight of the formulation.
  • antifoam agent may be present in an amount from about 0.01 wt % to about 0.1 wt %.
  • the seal swell agent used in the transmission fluid compositions described herein is selected from oil-soluble diesters, oil-soluble sulfones, and mixtures thereof.
  • the most suitable diesters include the adipates, azelates, and sebacates of C 8 -C 13 alkanols (or mixtures thereof), and the phthalates of C 4 -C 13 alkanols (or mixtures thereof).
  • Mixtures of two or more different types of diesters e.g., dialkyl adipates and dialkyl azelates, etc. can also be used.
  • Such materials include the n-octyl, 2-ethylhexyl, isodecyl, and tridecyl diesters of adipic acid, azelaic acid, and sebacic acid, and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters of phthalic acid.
  • esters which may give generally equivalent performance are polyol esters such as EMERY 2935, 2936, and 2939 esters from the Emery Group of Henkel Corporation and HATCOL 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322 polyol esters from Hatco Corporation.
  • Suitable sulfone seal swell agents are described in U.S. Pat. Nos. 3,974,081 and 4,029,587.
  • Lubrizol 730 additive (The Lubrizol Corporation) is understood to be a commercially-available sulfone type seal swell agent.
  • these products are employed at levels in the range of about 0.25 wt % to about 5 wt % in the finished transmission fluid. As a further example, they may be provided in an amount of about 0.25 wt % to about 1 wt %.
  • Suitable seal swell agents are the oil-soluble dialkyl esters of (i) adipic acid, (ii) sebacic acid, or (iii) phthalic acid.
  • the adipates and sebacates should be used in amounts in the range of from about 1 to about 15 wt % in the finished fluid. In the case of the phthalates, the levels in the transmission fluid should fall in the range of from about 1.5 to about 10 wt %.
  • the higher the molecular weight of the adipate, sebacate or phthalate the higher should be the treat rate within the foregoing ranges.
  • Additives used in formulating the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it is suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).
  • an additive concentrate i.e., additives plus a diluent, such as a hydrocarbon solvent.
  • the use of an additive concentrate takes advantage of the mutual compatibility afforded by the combination of ingredients when in the form of an additive concentrate. Also, the use of a concentrate reduces blending time and lessens the possibility of blending errors.
  • the power transmission fluids disclosed herein may include fluids suitable for any power transmitting application, such as a step automatic transmission or a manual transmission. Further, the power transmission fluids of the present disclosure are suitable for use in transmissions with a slipping torque converter, a lock-up torque converter, a starting clutch, and/or one or more shifting clutches. Such transmissions include four-, five-, six-, and seven-speed transmissions, and continuously variable transmissions (chain, belt, or disk type). They may also be used in manual transmissions, including automated manual and dual-clutch transmissions.
  • the standard test pin is AISI 3135 Steel, HRB 87 and the standard Vee Blocks are AISI C-1137 Steel, HRC 20 to 24.
  • the lubricant compositions were tested at 100° C. and 150° C. Higher loads to seizure signify better extreme pressure (EP) performance.
  • the baseline fluid contained the following components:
  • HiTEC® 611 detergent is an overbased calcium sulfonate available from Ethyl Corporation of Richmond, Va.
  • Zn phenate is zinc phenate.
  • HiTEC® 059 is a dimethyloctadecylphosphonate available from Ethyl Corporation. TABLE 1 HiTEC ® Falex EP Falex EP 611 HiTEC ® Fail Fail Fluid detergent Zn Phenate 059 load (lbs) @ load (lbs) @ No. (wt. %) (wt. %) (wt. %) 100° C. 150° C. 1 0.00 0.00 0.00 1250 1000 2 0.20 0.20 0.25 1250 1250 3 0.20 0.20 0.00 750 750 4 0.20 0.00 0.25 1000 750 5 0.00 0.00 0.25 2125 2000 6 0.00 0.20 0.00 750 500 7 0.00 0.20 0.25 2000 2000 8 0.20 0.00 0.00 1250 625
  • a baseline fluid absent an extreme pressure performance improving amount of ester of phosphonic acid had a seizure load of 1250 pounds at 100° C. and 1000 pounds at 150° C. (Fluid No. 1).
  • Much higher seizure loads were obtained with a baseline fluid containing an ester of phosphonic acid (Fluid Nos. 5 and 7) in the absence of a detergent containing calcium cations.
  • the fluids containing a detergent having a calcium cation (Fluid Nos. 3 and 8) gave worse performance, i.e., lower seizure loads, than the baseline fluid.
  • succinimide No. 1 was treated with 0.1 wt % amount of boron.
  • Succinimide No. 2 was treated with the same amount of boron and 1.3 wt % amount of nonyphenol and formaldehyde.
  • Succinimide No. 3 was treated the same as succinimide No.
  • succinimide post-treated with boron, nonylphenol/formaldehyde, and glycolic acid gave significantly higher Falex EP values than the succinimide treated with boron alone (Succinimide No. 1) and the succinimide treated with boron and nonylphenol/formaldehyde (Succinimide No. 2). It is expected that a post-treated succinimide treated with boron, nonlyphenol/formaldehyde, and glycolic acid, combined with a phosphonate according to the invention will achieve superior extreme pressure performance in a lubricant composition containing these components.
  • each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

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