WO2019133191A1 - Lubrification de surfaces de carbone de type diamant oxygéné - Google Patents

Lubrification de surfaces de carbone de type diamant oxygéné Download PDF

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WO2019133191A1
WO2019133191A1 PCT/US2018/063575 US2018063575W WO2019133191A1 WO 2019133191 A1 WO2019133191 A1 WO 2019133191A1 US 2018063575 W US2018063575 W US 2018063575W WO 2019133191 A1 WO2019133191 A1 WO 2019133191A1
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carbon
acid
diamond
group
metal
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Arben JUSUFI
Alan M. Schilowitz
Aditya Jaishankar
Andrew R. KONICEK
Ko Onodera
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Exxonmobil Research And Engineering Company
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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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/56—Boundary lubrication or thin film lubrication
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/04—Oxidation, e.g. ozonisation

Definitions

  • This disclosure relates to methods for reducing friction and/or wear during lubrication of diamond-like carbon surfaces.
  • DLC Diamond-like carbon
  • other new coating materials are growing in importance. Thin layers of these advanced materials are being used to enhance the friction and wear properties of materials in engines and other operating equipment. For example, DLC can provide a beneficial combination of a high hardness value while also having a low friction coefficient. The ability to lubricate these materials is an important factor for future lubricants.
  • U.S. Patent 8,846,590 describes methods for lubricating DLC surfaces using a lubricating oil that contains an oil-soluble organo-molybdenum compound selected from compounds that include a variety of ligands.
  • a lubricating oil that contains an oil-soluble organo-molybdenum compound selected from compounds that include a variety of ligands.
  • Various types of DLC surfaces are discussed, including surfaces containing substantial amounts of hydrogen, but oxygen is not mentioned as a potential element on the surface.
  • the reference describes that molybdenum friction reducers can be effective for reducing friction at DLC surfaces, but no discussion is provided regarding wear.
  • a method for lubricating a machine surface can include supplying a lubricant comprising a Group VI metal-containing friction modifier to a surface layer comprising diamond-like carbon with a surface oxygen to carbon ratio of 1 : 15 or more.
  • the lubricant can include 0.05 wt% to 0.2 wt% of the Group VI metal-containing friction modifier.
  • the Group VI metal-containing friction modifier can have a AG of adsorption on the diamond-like carbon of -25 kJ/mol or less.
  • Group VI metal-containing friction modifiers can include Mo-containing friction modifiers, such as molybdenum dithiophosphate (MoDTP) and/or friction modifiers including a trinuclear molybdenum core.
  • Mo-containing friction modifiers such as molybdenum dithiophosphate (MoDTP) and/or friction modifiers including a trinuclear molybdenum core.
  • the amount of Mo (or other Group VI metal) in the lubricant can be 50 wppm or more.
  • the Group VI metal-containing friction modifier can have a polar site diameter of 5.0 Angstroms or more, or 7.0 Angstroms or more.
  • the diamond-like carbon can correspond to borated diamond-like carbon where the ratio of boron to carbon is 0.5 : 100 or more. Additionally or alternately, the diamond-like carbon can have a surface oxygen to carbon ratio of 1 : 10 or more. The depth for determining the surface oxygen to carbon ratio can correspond to the top 1.0 nm of the surface, or optionally the top 0.7 nm. In some aspects, the diamond-like carbon can have a ratio of sp 2 to sp 3 hybridized carbons in the diamond-like carbon of 0.5 to 2.5, or 0.7 to 1.5.
  • FIG. 1 shows X-ray photoelectron spectroscopy (XPS) data for oxygen concentration relative to sputtering depth for a borated and oxygenated diamond-like carbon surface.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 2 shows XPS data for carbon concentration relative to sputtering depth for a borated and oxygenated diamond-like carbon surface.
  • FIG. 3 shows adsorption isotherms for MoDTP on various surfaces.
  • FIG. 4 shows adsorption isotherms for a trinuclear molybdenum compound made up of an M03S7 core on various surfaces.
  • FIG. 5 shows adsorption isotherms for MoDTC on various surfaces.
  • FIG. 6 shows friction coefficient and wear depth for a base formulated lubricant including various friction modifiers.
  • FIG. 7 shows the relationship of free energy of adsorption versus friction coefficient and wear depth for a base formulated lubricant including various friction modifiers.
  • FIG. 8 shows friction coefficient and wear depth relative to Mo concentration for a base formulated lubricant including various friction modifiers.
  • FIG. 9 shows adsorption isotherms for a trinuclear molybdenum compound made up of an M03S4 core on various surfaces.
  • minor amount or“minor component” as it relates to components included within the lubricating oils of the specification and the claims means less than 50 wt.%, or less than or equal to 40 wt.%, or less than or equal to 30 wt.%, or greater than or equal to 20 wt.%, or less than or equal to 10 wt.%, or less than or equal to 5 wt.%, or less than or equal to 2 wt.%, or less than or equal to 1 wt.%, based on the total weight of the lubricating oil.
  • phrases“essentially free” as it relates to components included within the lubricating oils of the specification and the claims means that the particular component is at 0 weight % within the lubricating oil, or alternatively is at impurity type levels within the lubricating oil (less than 100 ppm, or less than 20 ppm, or less than 10 ppm, or less than 1 ppm).
  • the phrase“other lubricating oil additives” as used in the specification and the claims means other lubricating oil additives that are not specifically recited in the particular section of the specification or the claims.
  • lubricating oil additives may include, but are not limited to, antioxidants, detergents, dispersants, antiwear additives, corrosion inhibitors, viscosity modifiers, metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, friction modifiers and combinations thereof.
  • a diamond- like carbon surface layer having a surface ratio of oxygen to carbon of 1 : 15 or more can be lubricated using a lubricant oil that includes a molybdenum-based friction modifier additive, a tungsten-based friction modifier additive, or a combination thereof.
  • the Mo-based friction modifier (and/or other friction modifier based on a Group VI metal) can be selected based on the Gibbs free energy of adsorption (AG) for the friction modifier on an oxygenated diamond-like carbon surface.
  • the Mo-based friction modifier can further be selected based on a characteristic diameter associated with the Mo-based compound, such as a molecular diameter and/or a polar diameter.
  • ETse of a Mo-based friction modifier (and/or other friction modifier based on a Group VI metal) having a sufficiently low AG of adsorption can reduce friction at the surface of the oxygenated diamond-like carbon while causing a reduced or minimized amount of wear during lubrication.
  • a sufficiently low AG of adsorption value can correspond to - 25 kJ/mol or less, or -28 kJ/mol or less, or -30 kJ/mol or less.
  • Diamond-like carbon is a potentially valuable type of coating for surfaces where having a high hardness, low friction material is desirable.
  • the friction coefficient of diamond-like carbon without lubrication can be relatively low depending on conditions, corresponding to about 0.16 or less.
  • attempting to further reduce this friction coefficient using a lubricant can be challenging.
  • Some challenges are due to conventional friction modifiers that simply do not provide a benefit on diamond-like carbon surfaces.
  • stearic acid is a known organic friction modifier used in lubricating oils for lubrication of steel surfaces and/or other surfaces. Unfortunately, stearic acid provides little or no reduction of the friction coefficient for diamond like carbon.
  • stearic acid has a low affinity for adsorption on a diamond-like carbon surface. This was determined based on attempts to characterize a Gibbs free energy of adsorption (AG) of stearic acid on to a diamond-like carbon surface. It was determined that the absolute value of AG for stearic acid adsorbing to the diamond-like carbon surface or the surface coverage was too small to measure.
  • AG Gibbs free energy of adsorption
  • Mo-based friction modifiers and/or other Group VI metal-based friction modifiers
  • the difficulties related to increased wear for Mo-based friction modifiers can be reduced or minimized for diamond-like carbon surfaces that are oxygenated diamond-like carbon surfaces.
  • Mo-based friction modifiers that have a sufficiently negative free energy of adsorption (AG) can be used to reduce the friction coefficient of the surface while reducing or minimizing the amount of wear.
  • the free energy of adsorption (AG) can represent an amount of affinity of a compound for a surface.
  • Adsorption of a molecule to a surface corresponds to a loss of one or more degrees of freedom of motion, and therefore it might be expected that adsorption of a molecule to a surface corresponds to a loss of entropy.
  • the enthalpy of adsorption (AH) has to be sufficiently negative to overcome any decrease in entropy (AS) caused by the adsorption.
  • Mo-based friction modifiers (or other friction modifiers based on a Group VI metal) with a AG value for adsorption of roughly -25 kJ/mol or lower, or -28 kJ/mol or lower, or -30 kJ/mol or lower, can reduce the friction coefficient of a diamond-like carbon surface without causing an undesirable level of surface wear.
  • the discovery that the free energy of adsorption is related to reducing or minimizing wear on oxygenated DLC surfaces is unexpected. The unexpected nature of this discovery is reinforced because the Mo-containing friction modifiers that have a desirable free energy of adsorption are different from the compounds that would be expected to reduce or minimize wear based on other factors.
  • suitable Group VI metal-based friction modifiers for oxygenated diamond-like carbon surfaces can also have a sufficiently large diameter. Without being bound by any particular theory, it is believed that the adsorption of Group VI metal-based friction modifiers to an oxygenated diamond-like carbon surface is based in part on adsorption related to oxygen sites on the surface. A friction modifier with a sufficiently large diameter can have a sufficient size to bridge the distance between oxygen sites on the surface. This can potentially correspond to a sufficiently large molecular diameter and/or a sufficiently large polar diameter.
  • an adsorption isotherm can be determined for a friction modifier on an oxygenated diamond-like carbon surface.
  • the oxygenated diamond-like carbon surface used for determining the adsorption isotherm can have an oxygen to carbon molar ratio of between 1 : 10 and 1 : 8.
  • Quartz Crystal Microbalance (QCM) experiments were performed on a commercially- available instrument from Biolin Scientific (QSense QCM-D, E4 flow cells). Hydrocarbon- resistant Kalrez o-rings and seals were used in the flow cells. The injection flow-rate was maintained at 150 uL/min using a peristaltic pump (Cole-Palmer). Solvent-resistant PVC solva tubing (Cole Palmer) was chosen for the peristaltic pump. Teflon inlet tubing and fittings were used as far as possible. The quartz sensors (Biolin Scientific) were coated with the material of interest. For example, diamond-like coatings of various types and thicknesses can be applied in the normal coating process used to apply them.
  • the BET model provides two values of free energy of adsorption - one corresponding to the first layer, and one corresponding to each subsequent multilayer. It is the free energy corresponding to adsorption of the first layer which is reported here and is used for measuring friction efficacy on oxygenated diamond like carbon. For most data the Langmuir and BET isotherms give similar results for delta G.
  • Molecular Diameter is equal to two times the Molecular Radius.
  • R molecular radius
  • R is defined as the average distance of all atoms in the molecule with respect to the configurational center of the molecule (not mass weighted).
  • Molecular radius can be calculated by any convenient method, such as based on published values or using commercial molecular modeling tools.
  • Polar Site Diameter The calculation for the polar site diameter, 2R P , is similar to that of Molecular Diameter but only accounts for the polar atoms within the friction modifier.
  • polar atoms are defined as a) transition metals, b) phosphorus atoms, and c) non-carbon and non-hydrogen atoms that have a bond to an atom different from carbon and hydrogen.
  • the molecular diameter of a minimized energy configuration for a molecule may be different from the time-averaged value, and may also depend on solvent effects.
  • the polar site diameter is expected to have a lower variation than molecular diameter with respect to such factors.
  • the polar site diameter of a Mo- containing friction modifier can be 7.0 Angstroms or more, or 7.2 Angstroms or more.
  • the amount of wear at an oxygenated diamond-like carbon surface can be determined by the following method. Reciprocating sliding tests were conducted using a High Frequency Reciprocating Rig (HFRR) ( PCS Instruments) ball-on-flat tribometer. Operating conditions were 50 Hz frequency, 100 g load, 50 °C oil bath temperature, 2.0 mm stroke length, and total test duration of 2 hours. The ball was held in a fixed position by a set screw to prevent rolling. Lubricant temperatures were equilibrated for 15 minutes before sliding began. The ball and disk were standard 52100 bearing steel, with nominal hardness values of 200 HV30 for the disk and 58-66 Rockwell C hardness for the ball. In order to evaluate friction and wear on diamond like carbon, disks were modified by depositing a coating of diamond like carbon. In all cases the balls were used as supplied without application of an additional surface coating.
  • HFRR High Frequency Reciprocating Rig
  • Wear on the HFRR disk at end of test was quantified by making linear height profiles across the width of the wear scar in three different locations. Profiles were made using a stylus profilometer (Veeco Dektak 150). The reported depth of the wear scar was quantified by averaging the lowest point in the center of the three line scans. In the claims, wear depth values correspond to wear depth values measured using a stylus profilometer. Reported friction is the average friction over the last 30 minutes of the test.
  • friction and wear were also measured with a Falex block on ring (LFW-l) machine with a load of 294N (Hertzian contact pressure of about 300MPa), a sliding velocity of 0.3m/s, an oil temperature of 80 C, and a sliding duration of 30 min. The lowest friction coefficients during test are reported.
  • the ring was SAE4620 steel while the block was steel coated with BDLC.
  • wear depth values were determined using an optical profilometer. The wear depths were measured at three points (center and two near edges) on the linear wear scar with SURFTEST SV-3200 (manufactured by Mitsutoyo). The three wear measurements are averaged. The optical values are believed to be comparable to wear depth values that would be obtained using a stylus profilometer.
  • Diamond-like carbon is an amorphous carbon material that can provide some physical properties that are similar to diamond.
  • the physical properties can include providing a high hardness value, such as a hardness value of 2 GPa or more, while also having a low friction coefficient, such as a friction coefficient of 0.16 or less prior to exposure to friction modifiers in a lubricating oil.
  • This combination of physical properties can potentially be beneficial for use of diamond-like carbon layers in various machine or tool applications. Without being bound by any particular theory, it is believed that the beneficial combination of properties in diamond-like carbon is due in part to combination of carbon atoms that participate in both a diamond like tetrahedral bonding network (sp 3 type bonding) and a graphitic (sp 2 type bonding) network.
  • diamond-like carbon is defined as an amorphous material that has a hardness value of 2 GPa or more and a hydrogen content of 10 mole% or more.
  • the hydrogen content can be 15 mole% or more, or 20 mole% or more, such as up to 40 mole% or possibly still higher.
  • Such a material can have 60 mole% or more (or 75% or more) of carbon atoms relative to the total atoms in the amorphous material aside from hydrogen.
  • the ratio of sp 2 carbon atoms to sp 3 hybridized carbon atoms can be between 0.5 and 2.5, or between 0.7 and 1.5.
  • Such an amorphous material can be present, for example, as a coating layer on another surface.
  • Diamond- like carbon can be in contrast to tetrahedral amorphous carbon, which has a hydrogen content of 10 mole% or less.
  • a diamond-like carbon layer can have a layer depth of 2.0 pm or more.
  • oxygenated diamond-like carbon can correspond to diamond-like carbon that includes a surface ratio of oxygen to carbon of 1 : 15 or more, such as 1 : 10 or more, or 1 : 8 or more, such as up to 1 : 5 or possibly still higher. Unless otherwise specified, this surface ratio can correspond to the ratio of oxygen to carbon in the top 1.0 nm at the surface. In some optional aspects, the surface ratio of 1 : 15 or more, or 1 : 10 or more, can correspond to the top 0.7 nm at the surface.
  • Having a surface ratio of oxygen to carbon of 1 : 15 or more can be beneficial for providing adsorption locations for an Mo-based friction modifier (or other Group VI metal-based friction modifier) to adsorb to during adsorption.
  • the ratio of oxygen to carbon deeper in a diamond-like carbon layer such as at 5 nm or more, or 2 nm or more, can be lower than the surface ratio.
  • the ratio of oxygen to carbon deeper in the layer can be 1 : 20 or less, or 1 : 30 or less, or 1 : 40 or less.
  • an oxygenated diamond-like carbon can correspond to a borated and oxygenated diamond-like carbon layer.
  • boron can be beneficial for allowing additional oxygen to be incorporated into the surface of a diamond-like carbon layer.
  • the ratio of boron atoms to carbon atoms in a borated diamond-like carbon layer can be 0.5 : 100 or more, or 1.0 : 100 or more, such as up to 5.0 : 100 or possibly still higher.
  • Molybdenum-based friction modifier additives are known to be effective as friction reducing additives for diamond-like carbon surfaces.
  • the increased wear that is conventionally believed to be caused by using Mo-based friction modifiers may make it difficult to commercially implement such additives.
  • a Mo- based friction modifier additive with a sufficiently negative free energy of adsorption (AG) can allow for use of a Mo-based friction modifier additive while reducing or minimizing associated wear of an oxygenated diamond-like carbon surface.
  • Group VI metal-based friction modifiers with a sufficiently negative free energy of adsorption can be used, such as friction modifiers including Mo, W, or a combination thereof.
  • the amount of Group VI metal-based friction modifier included in a lubricant can correspond to 50 wppm or more of the Group VI metal, or 100 wppm or more, or 200 wppm or more, or at least 300 wppm, or at least 500 wppm, or at least 800 wppm, such as up to 3000 wppm or possibly still higher.
  • Suitable Group VI metal -based friction modifiers can include commercially available Mo-containing compounds as well as other Mo-containing compounds known in the art, such as those described in U.S. Patent 8,846,590.
  • Mo-based friction reducing additives can be additives corresponding to molybdenum dithiophosphate (MoDTP), which is available commercially as Adeka Sakura Lube 300.
  • MoDTP molybdenum dithiophosphate
  • the carbon chain lengths in compounds referred to as MoDTP can vary, but the specific carbon chain lengths are not believed to be critical, so long as the MoDTP is soluble in the lubricating oil.
  • Examples of typical chain lengths for MoDTP can be from 3 carbons to 30 carbons.
  • MoDTC molybdenum dithiocarbamate
  • Adeka Sakura Lube 515 an example of a class of Mo-based friction reducing additives that does not have a sufficiently negative free energy of adsorption
  • MoDTC can also have a variety of carbon chain lengths, with the chain length not being critical so long as the MoDTC is souble in lubricating oil.
  • oxygenated borated diamond-like carbon the AG of adsorption for MoDTC is about -24.6kJ/mol, while the AG of adsorption for MoDTP is roughly - 35 kJ/mol on oxygenated borated diamond-like carbon.
  • Mo-based friction reducing additive with a sufficiently negative free energy of adsorption on oxygenated diamond-like carbon can correspond to compounds with a molybdenum-sulfur core having a stoichiometry of M03S4.
  • M03S4 compounds can include various ligands for charge balance.
  • An example of a suitable ligand can be dithiocarbamate (dtc).
  • An example of a friction modifier with a M03S4 core can be Mo3S4[(2-ethylhexyl)2dtc]4.
  • Mo-based friction reducing additive with a sufficiently low free energy of adsorption on oxygenated diamond-like carbon can correspond to compounds with a molybdenum- sulfur core having a stoichiometry of M03S7.
  • these types of compounds that include a molybdenum-sulfur core containing three molybdenum atoms are referred to as Mo- trimer compounds or trinuclear molybdenum compounds.
  • These Mo-trimer compounds / trinuclear molybdenum compounds can include various ligands for charge balance.
  • An example of a suitable ligand can be dithiocarbamate (dtc).
  • dtc dithiocarbamate
  • An example of one such commercially available Mo-trimer compound is Infmeum C9455B.
  • Mo- containing friction modifiers are chemically converted to molybdenum sulfide type compounds at a surface that is being lubricated.
  • molybdenum and sulfur containing friction modifiers are that, under lubricating conditions, the rubbing of the friction modifier between two hard surfaces induces a reaction which produces M0S2, a known solid lubricant.
  • M0S2 a known solid lubricant.
  • performance would be greatest for a friction modifier which most effectively covered the lubricated surface with M0S2. In order to investigate this point the following tests and analyses were conducted.
  • Three molybdenum containing compounds were blended into a polyalphaolefm-based lubricant at a concentration corresponding to 700 ppm by weight molybdenum and tested in a HFRR test, as further described herein.
  • the three molybdenum-containing compounds corresponded to MoDTC, MoDTP, and an Mo-trimer compound.
  • the wear scar on the steel disk was analyzed using a Raman Spectroscopy microscope to determine how much of the wear scar track was covered by M0S2 produced by rubbing on the friction modifier. Based on the Raman spectroscopy measurement, the M0S2 coverage for the lubricant containing the Mo-trimer corresponded to only 67% of the wear scar surface.
  • the M0S2 coverage for the MoDTC-containing lubricant was roughly 78%, while the coverage for the MoDTP-containing lubricant was roughly 79%. Based on this one would predict that MoDTC would have equal performance to MoDTP and both would perform better than the Mo-trimer. In contrast to this conventionally expected result, it has been discovered that wear performance is predicted by free energy of adsorption and/or by the size of the polar core. Based on free energy of adsorption, the MoDTC friction modifier results in undesirable amounts of wear, while the Mo-trimer and MoDTP friction modifiers can unexpectedly reduce or minimize wear on DLC surfaces.
  • Lubricating base oils that are useful in the present disclosure are natural oils, mineral oils and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefmed (the latter is also known as reclaimed or reprocessed oil).
  • Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
  • Groups I, II, III, IV and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stocks have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturates.
  • Group II base stocks have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates.
  • Group III stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03 % sulfur and greater than about 90% saturates.
  • Group IV includes polyalphaolefms (PAO).
  • Group V base stock includes base stocks not included in Groups I-IV. Table 1 below summarizes properties of each of these five groups.
  • the number average molecular weights of the PAOs typically vary from about 250 to about 3,000, although PAO’s may be made in viscosities up to about 150 cSt (l00°C).
  • the PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefms which include, but are not limited to, C2 to about C32 alphaolefms with the Cx to about Ci6 alphaolefms, such as l-octene, l-decene, l-dodecene and the like, being preferred.
  • alphaolefms such as l-octene, l-decene, l-dodecene and the like, being preferred.
  • the preferred polyalphaolefms are poly- l-octene, poly- l-decene and poly- l-dodecene and mixtures thereof and mixed olefin-derived polyolefins.
  • the PAO fluids may be conveniently made by the polymerization of an alphaolefm in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boro
  • Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof.
  • hydroisomerized waxy stocks e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • hydroisomerized Fischer-Tropsch waxes e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • Fischer-Tropsch waxes the high boiling point residues of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
  • the hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • an amorphous hydrocracking/hydroisomerization catalyst such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC specialized lube hydrocracking
  • a zeolitic catalyst preferably ZSM-48 as described in U.S. Patent No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety.
  • Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Patent Nos.
  • Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax- derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant disclosure, and may have useful kinematic viscosities at l00°C of about 2 cSt to about 50 cSt, preferably about 2 cSt to about 30 cSt, more preferably about 3 cSt to about 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about 4.0 cSt at l00°C and a viscosity index of about 141.
  • Gas-to-Liquids (GTL) base oils may have useful pour points of about -20°C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30°C to about -40°C or lower.
  • Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Patent Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and are incorporated herein in their entirety by reference.
  • Naphthalene or methyl naphthalene for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
  • Alkylated naphthalene and analogues may also comprise compositions with isomeric distribution of alkylating groups on the alpha and beta carbon positions of the ring structure.
  • Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York, 1963.
  • an aromatic compound such as benzene or naphthalene
  • an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964.
  • Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl- 1,3 -propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least about 4 carbon atoms, preferably Cs to C30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
  • the hindered polyols such as the neopentyl polyol
  • esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
  • Turbine oil formulations containing renewable esters are included in this disclosure.
  • the renewable content of the ester is typically greater than about 70 weight percent, preferably more than about 80 weight percent and most preferably more than about 90 weight percent.
  • Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
  • Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non- mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
  • GTL Gas-to-Liquids
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon- containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
  • GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed
  • GTL base stock(s) and/or base oil(s) derived from GTL materials are characterized typically as having kinematic viscosities at l00°C of from about 2 mm 2 /s to about 50 mm 2 /s (ASTM D445). They are further characterized typically as having pour points of -5°C to about -40°C or lower (ASTM D97). They are also characterized typically as having viscosity indices of about 80 to about 140 or greater (ASTM D2270).
  • the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffms and multicycloparaffms in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorus and aromatics make this materially especially suitable for the formulation of low SAP products.
  • the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
  • Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • Minor quantities of Group I stock such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an“as-received” basis.
  • Even in regard to the Group II stocks it is preferred that the Group II stock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range 100 ⁇ VI ⁇ 120.
  • the base oil constitutes the major component of the turbine oil lubricant composition of the present disclosure and typically is present in an amount ranging from about 80 to about 99.8 weight percent, preferably from about 90 to about 99.5 weight percent, and more preferably from about 95 to about 99 weight percent, based on the total weight of the composition.
  • the base oil may be selected from any of the synthetic or natural oils typically used as lubricating oils for industrial oils and turbomachines.
  • the base oil conveniently has a kinematic viscosity, according to ASTM standards, of about 7 cSt to about 46 cSt (or mm 2 /s) at 40°C and preferably of about 10 cSt to about 32 cSt (or mm 2 /s) at 40°C, often more preferably from about 15 cSt to about 22 cSt.
  • Mixtures of synthetic and natural base oils may be used if desired.
  • Bi-modal, tri-modal, and additional combinations of mixtures of Group I, II, III, IV, and/or V base stocks may be used if desired.
  • the co-base stock component is present in an amount sufficient for providing solubility, compatibility and dispersancy of polar additives in the lubricating oil.
  • the co-base stock component is present in the lubricating oils of this disclosure in an amount from about 1 to about 99 weight percent, preferably from about 5 to about 95 weight percent, and more preferably from about 10 to about 90 weight percent.
  • API Group III/III+ GTL 0- 100 3-95
  • EPC Ethylene-propylene copolymer
  • Olefin-esters e.g. Ketjenlube
  • ADPO Alkylated Diphenyl Oxide
  • the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the commonly used lubricating oil performance additives including but not limited to antiwear additives, dispersants, detergents, viscosity modifiers, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity modifiers, fluid-loss additives, seal compatibility agents, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • the commonly used lubricating oil performance additives including but not limited to antiwear additives, dispersants, detergents, viscosity modifiers, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity modifiers, fluid-loss additives, seal compatibility agents, lub
  • the additives useful in this disclosure do not have to be soluble in the lubricating oils. Insoluble additives in oil can be dispersed in the lubricating oils of this disclosure.
  • Alkyldithiophosphates, aryl phosphates and phosphites are illustrative antiwear additives useful in the lubricating oils of this disclosure.
  • the illustrative antiwear additives may be essentially free of metals, or they may contain metal salts.
  • a phosphate ester or salt is a phosphorus acid ester prepared by reacting one or more phosphorus acid or anhydride with a saturated alcohol.
  • the phosphorus acid or anhydride is generally an inorganic phosphorus reagent, such as phosphorus pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphorous acid, phosphoric acid, phosphorus halide, lower phosphorus esters, or a phosphorus sulfide, including phosphorus pentasulfide, and the like.
  • Lower phosphorus acid esters generally contain from 1 to about 7 carbon atoms in each ester group. Alcohols used to prepare the phosphorus acid esters or salts.
  • Examples of commercially available alcohols and alcohol mixtures include Alfol 1218 (a mixture of synthetic, primary, straight-chain alcohols containing 12 to 18 carbon atoms); Alfol 20+ alcohols (mixtures of C18 - C28 primary alcohols having mostly C20 alcohols as determined by GLC (gas-liquid-chromatography)); and Alfol22+ alcohols (Cl 8 - C28 primary alcohols containing primarily C22 alcohols).
  • Alfol alcohols are available from Continental Oil Company.
  • Another example of a commercially available alcohol mixture is Adol 60 (about 75% by weight of a straight chain C22 primary alcohol, about 15% of a C20 primary alcohol and about 8% of Cl 8 and C24 alcohols). The Adol alcohols are marketed by Ashland Chemical.
  • a variety of mixtures of monohydric fatty alcohols derived from naturally occurring triglycerides and ranging in chain length from C8 to Cl 8 are available from Procter & Gamble Company. These mixtures contain various amounts of fatty alcohols containing 12, 14, 16, or 18 carbon atoms.
  • CO-1214 is a fatty alcohol mixture containing 0.5% of C10 alcohol, 66.0% of C12 alcohol, 26.0% of C14 alcohol and 6.5% of C16 alcohol.
  • Neodol 23 is a mixture of C12 and C13 alcohols
  • Neodol 25 is a mixture of C12 to C15 alcohols
  • Neodol 45 is a mixture of C14 to C15 linear alcohols.
  • the phosphate contains from about 14 to about 18 carbon atoms in each hydrocarbyl group.
  • the hydrocarbyl groups of the phosphate are generally derived from a mixture of fatty alcohols having from about 14 up to about 18 carbon atoms.
  • the hydrocarbyl phosphate may also be derived from a fatty vicinal diol.
  • Fatty vicinal diols include those available from Ashland Oil under the general trade designation Adol 114 and Adol 158.
  • the former is derived from a straight chain alpha olefin fraction of Cl 1 - C14, and the latter is derived from a C15 - C18 fraction.
  • the phosphate salts may be prepared by reacting an acidic phosphate ester with an amine compound or a metallic base to form an amine or a metal salt.
  • the amines may be monoamines or polyamines. Useful amines include those amines disclosed in U.S. Patent No. 4,234,435.
  • Illustrative monoamines generally contain a hydrocarbyl group which contains from 1 to about 30 carbon atoms, or from 1 to about 12, or from 1 to about 6.
  • Examples of primary monoamines useful in the present disclosure include methylamine, ethylamine, propylamine, butylamine, cyclopentylamine, cyclohexylamine, octylamine, dodecylamine, allylamine, cocoamine, stearylamine, and laurylamine.
  • secondary monoamines examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclopentylamine, dicyclohexylamine, methylbutylamine, ethylhexylamine, etc.
  • An amine is a fatty (C8 - C30) amine which includes n-octylamine, n-decylamine, n- dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, oleyamine, etc.
  • R is a divalent alkylene group having about 2 to about 6 carbon atoms; x is a number from one to about 150, or from about one to about five, or one; and R" is a hydrocarbyl group of about 5 to about 150 carbon atoms.
  • An example of an ether amine is available under the name SURF AM® amines produced and marketed by Mars Chemical Company, Atlanta, Ga. Preferred etheramines are exemplified by those identified as SURFAM P14B (decyloxypropylamine), SURF AM P16A (linear C16), SURFAM P17B (tridecyloxypropylamine).
  • the carbon chain lengths (i.e., C14, etc.) of the SURF AMS described above and used hereinafter are approximate and include the oxygen ether linkage.
  • amine mixtures of this type are "Primene 81R” which is a mixture of Cl 1 - C14 tertiary alkyl primary amines and "Primene JMT” which is a similar mixture of Cl 8 - C22 tertiary alkyl primary amines (both are available from Rohm and Haas Company).
  • the tertiary aliphatic primary amines and methods for their preparation are known to those of ordinary skill in the art.
  • Another illustrative amine is a heterocyclic polyamine.
  • Preferred heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.
  • Piperidine, aminoalkyl substituted piperidines, piperazine, aminoalkyl substituted piperazines, morpholine, aminoalkyl substituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines are especially preferred.
  • the aminoalkyl substituents are substituted on a nitrogen atom forming part of the hetero ring.
  • heterocyclic amines include N- aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-diaminoethylpiperazine.
  • Hydroxy heterocyclic polyamines are also useful. Examples include N-(2-hydroxyethyl)cyclohexylamine, 3 -hydroxy cyclopentylamine, parahydroxyaniline, N-hydroxyethylpiperazine, and the like.
  • the metal salts of the phosphorus acid esters are prepared by the reaction of a metal base with the acidic phosphorus ester.
  • the metal base may be any metal compound capable of forming a metal salt.
  • metal bases include metal oxides, hydroxides, carbonates, sulfates, borates, or the like.
  • the metals of the metal base include Group IA, IIA, IB through VIIB, and VIII metals (CAS version of the Periodic Table of the Elements). These metals include the alkali metals, alkaline earth metals and transition metals.
  • the metal is a Group IIA metal, such as calcium or magnesium, Group IIB metal, such as zinc, or a Group VIIB metal, such as manganese.
  • the metal is magnesium, calcium, manganese or zinc.
  • metal compounds which may be reacted with the phosphorus acid include zinc hydroxide, zinc oxide, copper hydroxide, copper oxide, etc.
  • the fatty carboxylic acids are generally mixtures of straight and branched chain fatty carboxylic acids containing about 8 to about 30 carbon atoms, or from about 12 to about 24, or from about 16 to about 18.
  • Carboxylic acids include the polycarboxylic acids or carboxylic acids or anhydrides having from 2 to about 4 carbonyl groups, preferably 2.
  • the polycarboxylic acids include succinic acids and anhydrides and Diels-Alder reaction products of unsaturated monocarboxylic acids with unsaturated carboxylic acids (such as acrylic, methacrylic, maleic, fumaric, crotonic and itaconic acids).
  • the fatty carboxylic acids are fatty monocarboxylic acids, having from about 8 to about 30, preferably about 12 to about 24 carbon atoms, such as octanoic, oleic, stearic, linoleic, dodecanoic, and tall oil acids, preferably stearic acid.
  • the fatty carboxylic acid is reacted with at least one polyamine.
  • the polyamines may be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of the polyamines include alkylene polyamines and heterocyclic polyamines.
  • the lubricating oils of this disclosure can contain at least one phosphorus containing antiwear additive.
  • additives are amine phosphate antiwear additives such as that known under the trade name IRGALEIBE 349 and/or triphenyl phosphorothionate antiwear additives such as that known under the trade name IRGALETBE TPPT.
  • amine phosphates may be present in an amount of from 0.01 to 2%, preferably 0.2 to 1.5% by weight of the lubricant composition while such phosphorothionates are suitably present in an amount of from 0.01 to 3%, preferably 0.5 to 1.5% by weight of the lubricant composition.
  • a mixture of an amine phosphate and phosphorothionate may be employed.
  • Phosphates for use in the present disclosure include phosphates, acid phosphates, phosphites and acid phosphites.
  • the phosphates include triaryl phosphates, trialkyl phosphates, trialkylaryl phosphates, triarylalkyl phosphates and trialkenyl phosphates.
  • triphenyl phosphate tricresyl phosphate, benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate, ethylphenyldiphenyl phosphate, diethylphenylphenyl phosphate, propylphenyldiphenyl phosphate, dipropylphenylphenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, dibutylphenylphenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri(2-ethylhexyl) phosphate, tridecyl phosphate
  • the acid phosphates include, for example, 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, and isostearyl acid phosphate.
  • the phosphites include, for example, triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl) phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl phosphite.
  • the acid phosphites include, for example, dibutyl hydrogenphosphite, dilauryl hydrogenphosphite, dioleyl hydrogenphosphite, distearyl hydrogenphosphite, and diphenyl hydrogenphosphite.
  • Amines that form amine salts with such phosphates include, for example, mono- substituted amines, di-substituted amines and tri- substituted amines.
  • the mono- substituted amines include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine and benzylamine; and those of the di-substituted amines include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanolamine.
  • tri -substituted amines examples include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triethanolamine, and tripropanolamine.
  • Phosphates or their amine salts are added to the base oil in an amount from zero to 5% by weight, preferably from 0.1 to 2% by weight, relative to the total weight of the composition.
  • Illustrative carboxylic acids to be reacted with amines include, for example, aliphatic carboxylic acids, dicarboxylic acids (dibasic acids), and aromatic carboxylic acids.
  • the aliphatic carboxylic acids have from 8 to 30 carbon atoms, and may be saturated or unsaturated, and linear or branched.
  • aliphatic carboxylic acids include pelargonic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, eicosanoic acid, behenic acid, triacontanoic acid, caproleic acid, undecylenic acid, oleic acid, linolenic acid, erucic acid, and linoleic acid.
  • dicarboxylic acids include octadecylsuccinic acid, octadecenylsuccinic acid, adipic acid, azelaic acid, and sebacic acid.
  • aromatic carboxylic acids is salicylic acid.
  • Illustrative amines to be reacted with carboxylic acids include, for example, polyalkylene-polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, dipropylenetriamine, tetrapropylenepentamine, and hexabutyleneheptamine; and alkanolamines such as monoethanol amine and diethanolamine.
  • alkanolamines such as monoethanol amine and diethanolamine.
  • Reaction products of carboxylic acids and amines may added to the base oil in an amount of from zero to 5% by weight, preferably from 0.03 to 3% by weight, relative to the total weight of the composition.
  • illustrative antiwear additives include phosphites, thiophosphites, phosphates, and thiophosphates, including mixed materials having, for instance, one or two sulfur atoms, i.e., monothio- or dithio compounds.
  • 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.
  • phosphites and thiophosphites within the scope of the disclosure include phosphorous acid, mono-, di-, or tri-thiophosphorous acid, mono-, di-, or tri propyl phosphite or mono-, di-, or tri-thiophosphite; mono-, di-, or tri-butyl phosphite or mono-, di-, or tri-thiophosphite; mono-, di-, or tri-amyl phosphite or mono-, di-, or tri-thiophosphite; mono-, di-, or tri-hexyl phosphite or mono-, di-, or tri-thiophosphite; mono-, di-, or tri-phenyl phosphite or mono-, di-, or tri-thiophosphite; mono-, di-, or tri-tolyl phosphite or mono-, di-,
  • phosphates and thiophosphates within the scope of the disclosure include phosphoric acid, mono-, di-, or tri-thiophosphoric acid, mono-, di-, or tri-propyl phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, or tri-butyl phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, or tri-amyl phosphate or mono-, di-, or tri-thiophosphate; mono-, di- , or tri-hexyl phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, or tri-phenyl phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, ortritolyl phosphate or mono-, di-, ortrithiophosphate; mono-, di-, or tri-cresyl phosphate or mono-, di-, or tri-thiophosphate;
  • These phosphorus compounds may be prepared by well known reactions. One route the reaction of an alcohol or a phenol with phosphorus trichloride or by a transesterification reaction. Alcohols and phenols can be reacted with phosphorus pentoxide to provide a mixture of an alkyl or aryl phosphoric acid and a dialkyl or diaryl phosphoric acid. Alkyl phosphates can also be prepared by the oxidation of the corresponding phosphites. Thiophosphates can be prepared by the reaction of phosphites with elemental sulfur. In any case, the reaction can be conducted with moderate heating. Moreover, various phosphorus esters can be prepared by reaction using other phosphorus esters as starting materials.
  • medium chain (C9 to C22) phosphorus esters have been prepared by reaction of dimethylphosphite with a mixture of medium-chain alcohols by means of a thermal transesterification or an acid- or base-catalyzed transesterification. See, for example, U.S. Patent No. 4,652,416. Most such materials are also commercially available; for instance, triphenyl phosphite is available from Albright and Wilson as Duraphos TPPTM; di-n-butyl hydrogen phosphite from Albright and Wilson as Duraphos DBHPTM; and triphenylthiophosphate from Ciba Specialty Chemicals as Irgalube TPPTTM.
  • esters of the dialkylphosphorodithioic acids include esters obtained by reaction of the dialkyl phosphorodithioic acid with an alpha, beta-unsaturated carboxylic acid (e.g., methyl acrylate) and, optionally an alkylene oxide such as propylene oxide.
  • an alpha, beta-unsaturated carboxylic acid e.g., methyl acrylate
  • an alkylene oxide such as propylene oxide
  • One or more of the above-identified metal dithiophosphates may be used from about zero to about 2% by weight, and more generally from about 0.1 to about 1% by weight, based on the weight of the total composition.
  • the hydrocarbyl in the dithiophosphate may be alkyl, cycloalkyl, aralkyl or alkaryl groups, or a substantially hydrocarbon group of similar structure.
  • Illustrative alkyl groups include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl groups, n-hexyl, methylisobutyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
  • Illustrative lower alkylphenyl groups include butylphenyl, amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewise are useful and these include chiefly cyclohexyl and the lower alkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may also be used, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.
  • the phosphorodithioic acids are prepared by the reaction of a phosphorus sulfide with an alcohol or phenol or mixtures of alcohols.
  • a typical reaction involves four moles of the alcohol or phenol and one mole of phosphorus pentasulfide, and may be carried out within the temperature range from about 50°C to about 200°C.
  • the preparation of O,O-di-n-hexyl phosphorodithioic acid involves the reaction of a mole of phosphorus pentasulfide with four moles of n-hexyl alcohol at about l00°C for about two hours. Hydrogen sulfide is liberated and the residue is the desired acid.
  • the preparation of the metal salts of these acids may be effected by reaction with metal compounds as well known in the art.
  • the metal salts of dihydrocarbyldithiophosphates which are useful in this disclosure include those salts containing Group I metals, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt, and nickel.
  • the Group II metals, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel and copper are among the preferred metals. Zinc and copper are especially useful metals.
  • metal compounds which may be reacted with the acid include lithium oxide, lithium hydroxide, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, silver oxide, magnesium oxide, magnesium hydroxide, calcium oxide, zinc hydroxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, barium oxide, aluminum oxide, iron carbonate, copper hydroxide, lead hydroxide, tin butylate, cobalt hydroxide, nickel hydroxide, nickel carbonate, and the like.
  • the incorporation of certain ingredients such as small amounts of the metal acetate or acetic acid in conjunction with the metal reactant will facilitate the reaction and result in an improved product.
  • certain ingredients such as small amounts of the metal acetate or acetic acid in conjunction with the metal reactant
  • the use of up to about 5% of zinc acetate in combination with the required amount of zinc oxide facilitates the formation of a zinc phosphorodithioate with potentially improved performance properties.
  • Especially useful metal phosphorodithloates can be prepared from phosphorodithloic acids which in turn are prepared by the reaction of phosphorus pentasulfide with mixtures of alcohols.
  • the use of such mixtures enables the utilization of less expensive alcohols which individually may not yield oil-soluble phosphorodithioic acids.
  • a mixture of isopropyl and hexylalcohols can be used to produce a very effective, oil-soluble metal phosphorodithioate.
  • mixtures of phosphorodithioic acids can be reacted with the metal compounds to form less expensive, oil-soluble salts.
  • the mixtures of alcohols may be mixtures of different primary alcohols, mixtures of different secondary alcohols or mixtures of primary and secondary alcohols.
  • useful mixtures include: n-butanol and n-octanol; n-pentanol and 2-ethyl-l-hexanol; isobutanol and n- hexanol; isobutanol and isoamyl alcohol; isopropanol and 2-methyl-4-pentanol; isopropanol and sec-butyl alcohol; isopropanol and isooctyl alcohol; and the like.
  • Organic triesters of phosphorus acids are also employed in lubricants.
  • Typical esters include triarylphosphates, trialkyl phosphates, neutral alkylaryl phosphates, alkoxyalkyl phosphates, triaryl phosphite, trialkylphosphite, neutral alkyl aryl phosphites, neutral phosphonate esters and neutral phosphine oxide esters.
  • the long chain dialkyl phosphonate esters are used. More prferentially, the dimethyl-, diethyl-, and dipropyl-oleyl phohphonates can be used.
  • Neutral acids of phosphorus acids are the triesters rather than an acid (HO-P) or a salt of an acid.
  • Any C4 to C8 alkyl or higher phosphate ester may be employed in the disclosure.
  • tributyl phosphate (TBP) and tri isooctal phosphate (TOF) can be used.
  • TBP tributyl phosphate
  • TOF tri isooctal phosphate
  • the specific triphosphate ester or combination of esters can easily be selected by one skilled in the art to adjust the density, viscosity etc. of the formulated fluid.
  • Mixed esters, such as dibutyl octyl phosphate or the like may be employed rather than a mixture of two or more trialkyl phosphates.
  • a trialkyl phosphate is often useful to adjust the specific gravity of the formulation, but it is desirable that the specific trialkyl phosphate be a liquid at low temperatures. Consequently, a mixed ester containing at least one partially alkylated with a C3 to C4 alkyl group is very desirable, for example, 4-isopropylphenyl diphenyl phosphate or 3-butylphenyl diphenyl phosphate. Even more desirable is a triaryl phosphate produced by partially alkylating phenol with butylene or propylene to form a mixed phenol which is then reacted with phosphorus oxychloride as taught in U.S. Patent No. 3,576,923.
  • Any mixed triaryl phosphate (TAP) esters may be used as cresyl diphenyl phosphate, tricresyl phosphate, mixed xylyl cresyl phosphates, lower alkylphenyl/phenyl phosphates, such as mixed isopropylphenyl/phenyl phosphates, t-butylphenyl phenyl phosphates.
  • TEP triaryl phosphate
  • a metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate can be a useful component of the lubricating oils of this disclosure.
  • ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof.
  • ZDDP compounds generally are of the formula
  • R 1 and R 2 are Cl - C18 alkyl groups, preferably C2 - C12 alkyl groups. These alkyl groups may be straight chain or branched.
  • Alcohols used in the ZDDP can be propanol, 2- propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n- hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be preferred. Alkyl aryl groups may also be used.
  • Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations“LZ 677A”,“LZ 1095” and“LZ 1371”, from for example Chevron Oronite under the trade designation“OLOA 262” and from for example Afton Chemical under the trade designation“HITEC 7169”.
  • ZDDP is typically used in amounts of from about zero to about 3 weight percent, preferably from about 0.05 weight percent to about 2 weight percent, more preferably from about 0.1 weight percent to about 1.5 weight percent, and even more preferably from about 0.1 weight percent to about 1 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously.
  • a secondary ZDDP may be preferred and present in an amount of from zero to 1 weight percent of the total weight of the lubricating oil.
  • Extreme pressure agents and sulfur-based extreme pressure agents such as sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates, sulfurized fats and oils, sulfurized olefins and the like; phosphorus-based extreme pressure agents, such as phosphoric acid esters (e.g., tricresyl phosphate (TCP) and the like), phosphorous acid esters, phosphoric acid ester amine salts, phosphorous acid ester amine salts, and the like; halogen-based extreme pressure agents, such as chlorinated hydrocarbons and the like; organometallic extreme pressure agents, such as thiophosphoric acid salts (e.g., zinc dithiophosphate (ZnDTP) and the like) and thiocarbamic acid salts; and the like can be used.
  • phosphoric acid esters e.g., tricresyl phosphate (TCP) and the like
  • TCP tricre
  • the phosphoric acid ester, thiophosphoric acid ester, and amine salt thereof functions to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents.
  • phosphoric acid esters, a thiophosphoric acid ester, or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
  • Examples of the phosphoric acid esters include aliphatic phosphoric acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2- ethylhexyl phosphate, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate; and aromatic phosphoric acid esters such as benzyl phenyl phosphate, allyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, diprop
  • thiophosphoric acid esters examples include aliphatic thiophosphoric acid esters such as triisopropyl thiophosphate, tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearyl thiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoric acid esters such as benzyl phenyl thiophosphate, allyl diphenyl thiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyl diphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl thiophosphate, ethylphenyl diphenyl thiophosphate, diethylpheny
  • amine salts of the above-mentioned phosphates and thiophosphates are also employable.
  • the amine salt is an amine salt of trialkylphenyl phosphate or an amine salt of alkyl phosphate.
  • One or any combination of the compounds selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine salt thereof may be used.
  • the phosphorus acid ester and/or its amine salt function to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents. Generally employed is a phosphorus acid ester or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
  • Examples of the phosphorus acid esters include aliphatic phosphorus acid esters such as triisopropyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, trihexyl phosphite, tri-2- ethylhexylphosphite, trilauryl phosphite, tristearyl phosphite, and trioleyl phosphite; and aromatic phosphorus acid esters such as benzyl phenyl phosphite, allyl diphenylphosphite, triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl phosphite, dicresy
  • dilauryl phosphite dioleyl phosphite, dialkyl phosphites, and diphenyl phosphite.
  • the phosphorus acid ester is a dialkyl phosphite or a trialkyl phosphite.
  • the phosphate salt may be derived from a polyamine.
  • the polyamines include alkoxylated diamines, fatty polyamine diamines, alkylenepolyamines, hydroxy containing polyamines, condensed polyamines arylpolyamines, and heterocyclic polyamines. Examples of these amines include Ethoduomeen T/13 and T/20 which are ethylene oxide condensation products of N-tallowtrimethylenediamine containing 3 and 10 moles of ethylene oxide per mole of diamine, respectively.
  • the polyamine is a fatty diamine.
  • the fatty diamines include mono- or dialkyl, symmetrical or asymmetrical ethylene diamines, propane diamines (1,2 or 1,3), and polyamine analogs of the above.
  • Suitable commercial fatty polyamines are Duomeen C (N- coco-l,3-diaminopropane), Duomeen S (N-soya-l,3-diaminopropane), Duomeen T (N-tallow-l,3- diaminopropane), and Duomeen O (N-oleyl-l,3-diaminopropane).
  • Duomeens are commercially available from Armak Chemical Co., Chicago, Ill.
  • Such alkylenepolyamines include methylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, pentylenepolyamines, etc.
  • the higher homologs and related heterocyclic amines such as piperazines and N-amino alkyl-substituted piperazines are also included.
  • Specific examples of such polyamines are ethylenediamine, triethylenetetramine, tris- (2-aminoethyl)amine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, pentaethylenehexamine, etc.
  • Higher homologs obtained by condensing two or more of the above-noted alkyleneamines are similarly useful as are mixtures of two or more of the aforedescribed polyamines.
  • the polyamine is an ethylenepolyamine.
  • ethylenepolyamine Such polyamines are described in detail under the heading Ethylene Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965). Ethylenepolyamines are often a complex mixture of polyalkylenepolyamines including cyclic condensation products.
  • alkylenepolyamine bottoms can be characterized as having less than 2%, usually less than 1% (by weight) material boiling below about 200°C.
  • E-100 A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Tex. designated "E-100".
  • alkylenepolyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.
  • alkylenepolyamine bottoms can be reacted solely with the acylating agent or they can be used with other amines, polyamines, or mixtures thereof.
  • Another useful polyamine is a condensation reaction between at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group.
  • the hydroxy compounds are preferably polyhydric alcohols and amines. The polyhydric alcohols are described below. In one embodiment, the hydroxy compounds are polyhydric amines.
  • Polyhydric amines include any of the above-described monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) having from two to about 20 carbon atoms, or from two to about four.
  • alkylene oxide e.g., ethylene oxide, propylene oxide, butylene oxide, etc.
  • polyhydric amines examples include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-amino-2- methyl-l, 3 -propanediol, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and N,N,N',N'- tetrakis(2-hydroxyethyl)ethylenediamine, preferably tris(hydroxymethyl)aminomethane (TELAM).
  • TLAM tris(hydroxymethyl)aminomethane
  • Polyamines which react with the polyhydric alcohol or amine to form the condensation products or condensed amines are described above.
  • Preferred polyamines include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures of polyamines such as the above-described "amine bottoms”.
  • extreme pressure additives include sulphur-based extreme pressure additives such as dialkyl sulphides, dibenzyl sulphide, dialkyl polysulphides, dibenzyl disulphide, alkyl mercaptans, dibenzothiophene and 2,2'-dithiobis(benzothiazole); phosphorus-based extreme pressure additives such as trialkyl phosphates, triaryl phosphates, trialkyl phosphonates, trialkyl phosphites, triaryl phosphites and dialkylhydrozine phosphites, and phosphorus- and sulphur- based extreme pressure additives such as zinc dialkyldithiophosphates, dialkylthiophosphoric acid, trialkyl thiophosphate esters, acidic thiophosphate esters and trialkyl trithiophosphates. Extreme pressure additives can be used individually or in the form of mixtures, conveniently in an amount within the range from zero to 2
  • Dispersants During machine operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants used in the formulation of the lubricating oil may be ashless or ash-forming in nature. Preferably, the dispersant is ashless. So called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • a particularly useful class of dispersants are the (poly)alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
  • Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants are U.S. Patent Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542;
  • Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants.
  • succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
  • Succinimides are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA can vary from about 1 : 1 to about 5:1. Representative examples are shown in U.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1,094,044.
  • Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in U.S. Patent No. 4,426,305.
  • the molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.
  • the above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. Patent No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HNR2 group-containing reactants.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Patent Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084, 197.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis- succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from about 500 to about 5000, or from about 1000 to about 3000, or about 1000 to about 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components.
  • Polymethacrylate or polyacrylate derivatives are another class of dispersants. These dispersants are typically prepared by reacting a nitrogen containing monomer and a methacrylic or acrylic acid esters containing 5 - 25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2,100,993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are normally used as multifunctional viscosity modifiers. The lower molecular weight versions can be used as lubricant dispersants or fuel detergents.
  • Illustrative preferred dispersants useful in this disclosure include those derived from polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester, which dispersant has a polyalkenyl moiety with a number average molecular weight of at least 900 and from greater than 1.3 to 1.7, preferably from greater than 1.3 to 1.6, most preferably from greater than 1.3 to 1.5, functional groups (mono- or dicarboxylic acid producing moieties) per polyalkenyl moiety (a medium functionality dispersant).
  • Functionality (F) can be determined according to the following formula:
  • SAP is the saponification number (i.e., the number of milligrams of KOH consumed in the complete neutralization of the acid groups in one gram of the succinic-containing reaction product, as determined according to ASTM D94); M n is the number average molecular weight of the starting olefin polymer; and A.I. is the percent active ingredient of the succinic-containing reaction product (the remainder being unreacted olefin polymer, succinic anhydride and diluent).
  • the polyalkenyl moiety of the dispersant may have a number average molecular weight of at least 900, suitably at least 1500, preferably between 1800 and 3000, such as between 2000 and 2800, more preferably from about 2100 to 2500, and most preferably from about 2200 to about 2400.
  • the molecular weight of a dispersant is generally expressed in terms of the molecular weight of the polyalkenyl moiety. This is because the precise molecular weight range of the dispersant depends on numerous parameters including the type of polymer used to derive the dispersant, the number of functional groups, and the type of nucleophilic group employed.
  • Polymer molecular weight can be determined by various known techniques.
  • One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979).
  • GPC gel permeation chromatography
  • Another useful method for determining molecular weight, particularly for lower molecular weight polymers is vapor pressure osmometry (e.g., ASTM D3592).
  • the polyalkenyl moiety in a dispersant preferably has a narrow molecular weight distribution (MWD), also referred to as polydispersity, as determined by the ratio of weight average molecular weight (M w ) to number average molecular weight (M n ).
  • MWD molecular weight distribution
  • M w weight average molecular weight
  • M n number average molecular weight
  • Suitable polymers have a polydispersity of from about 1.5 to 2.1, preferably from about 1.6 to about 1.8.
  • Suitable polyalkenes employed in the formation of the dispersants include homopolymers, interpolymers or lower molecular weight hydrocarbons.
  • One family of such polymers comprise polymers of ethylene and/or at least one C3 to C26 alpha-olefin having the formula
  • R 1 is a straight or branched chain alkyl radical comprising 1 to 26 carbon atoms and wherein the polymer contains carbon-to-carbon unsaturation, and a high degree of terminal ethenylidene unsaturation.
  • such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein R 1 is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably still of from 1 to 2 carbon atoms.
  • Another useful class of polymers is polymers prepared by cationic polymerization of monomers such as isobutene and styrene.
  • monomers such as isobutene and styrene.
  • Common polymers from this class include polyisobutenes obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75% by wt., and an isobutene content of 30 to 60% by wt.
  • a preferred source of monomer for making poly-n-butenes is petroleum feedstreams such as Raffinate II. These feedstocks are disclosed in the art such as in U.S. Pat. No. 4,952,739.
  • a preferred embodiment utilizes polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
  • Polyisobutene polymers that may be employed are generally based on a polymer chain of from 1500 to 3000.
  • the dispersant(s) are preferably non-polymeric (e.g., mono- or bis-succinimides). Such dispersants can be prepared by conventional processes such as disclosed in U.S. Patent Application Publication No. 2008/0020950, the disclosure of which is incorporated herein by reference.
  • the dispersant(s) can be borated by conventional means, as generally disclosed in U.S. Patent Nos. 3,087,936, 3,254,025 and 5,430,105.
  • Dispersants may be used in an amount of zero to 10 weight percent or 0.01 to 8 weight percent, preferably about 0.1 to 5 weight percent, or more preferably 0.5 to 3 weight percent. Or such dispersants may be used in an amount of zero to 8 weight percent, preferably about 0.01 to 5 weight percent, or more preferably 0.1 to 3 weight percent. On an active ingredient basis, such additives may be used in an amount of zero to 10 weight percent, preferably about 0.3 to 3 weight percent.
  • the hydrocarbon portion of the dispersant atoms can range from C60 to Cl 000, or from C70 to C300, or from C70 to C200. These dispersants may contain both neutral and basic nitrogen, and mixtures of both.
  • Dispersants can be end-capped by borates and/or cyclic carbonates.
  • Nitrogen content in the finished oil can vary from about zero to about 2000 ppm by weight, preferably from about 100 ppm by weight to about 1200 ppm by weight.
  • Basic nitrogen can vary from about zero to about 1000 ppm by weight, preferably from about 100 ppm by weight to about 600 ppm by weight.
  • the dispersant concentrations are given on an“as delivered” basis.
  • the active dispersant is delivered with a process oil.
  • The“as delivered” dispersant typically contains from about 20 weight percent to about 80 weight percent, or from about 40 weight percent to about 60 weight percent, of active dispersant in the“as delivered” dispersant product.
  • Illustrative detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents.
  • a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
  • the anionic portion of the detergent is typically derived from an organic acid such as a sulfur-containing acid, carboxylic acid (e.g., salicylic acid), phosphorus-containing acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • the detergent can be overbased as described herein.
  • the detergent is preferably a metal salt of an organic or inorganic acid, a metal salt of a phenol, or mixtures thereof.
  • the metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof.
  • the organic or inorganic acid is selected from an aliphatic organic or inorganic acid, a cycloaliphatic organic or inorganic acid, an aromatic organic or inorganic acid, and mixtures thereof.
  • the metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof. More preferably, the metal is selected from calcium (Ca), magnesium (Mg), and mixtures thereof.
  • the organic acid or inorganic acid is preferably selected from a sulfur-containing acid, a carboxylic acid, a phosphorus-containing acid, and mixtures thereof.
  • the metal salt of an organic or inorganic acid or the metal salt of a phenol comprises calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate, an overbased detergent, and mixtures thereof.
  • Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • Useful detergents can be neutral, mildly overbased, or highly overbased. These detergents can be used in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates, phenates and/or magnesium salicylate, sulfonates, phenates.
  • the TBN ranges can vary from low, medium to high TBN products, including as low as 0 to as high as 600.
  • the TBN delivered by the detergent is between 1 and 20. More preferably between 1 and 12.
  • Mixtures of low, medium, high TBN can be used, along with mixtures of calcium and magnesium metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates.
  • a detergent mixture with a metal ratio of 1, in conjunction of a detergent with a metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used. Borated detergents can also be used.
  • Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example) with an alkyl phenol or sulfurized alkylphenol.
  • alkyl phenol or sulfurized alkylphenol include straight chain or branched Cl - C30 alkyl groups, preferably, C4 - C20 or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like.
  • starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched and can be used from 0.5 to 6 weight percent.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
  • sulfurizing agent including elemental sulfur, sulfur halides such as sulfur dichloride, and the like
  • metal salts of carboxylic acids are preferred detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Useful salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • R is an alkyl group having 1 to about 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least Cl 1, preferably C13 or greater.
  • R may be optionally substituted with substituents that do not interfere with the detergent’s function.
  • M is preferably, calcium, magnesium, barium, or mixtures thereof. More preferably, M is calcium.
  • Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction (see U.S. Patent No. 3,595,791).
  • the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
  • Alkaline earth metal phosphates are also used as detergents and are known in the art.
  • Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. Patent No. 6,034,039.
  • Preferred detergents include calcium sulfonates, magnesium sulfonates, calcium salicylates, magnesium salicylates, calcium phenates, magnesium phenates, and other related components (including borated detergents), and mixtures thereof.
  • Preferred mixtures of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium salicylate, calcium phenate and magnesium phenate.
  • Overbased detergents are also preferred.
  • Viscosity modifiers also known as viscosity index improvers (VI improvers), and viscosity improvers
  • VI improvers viscosity index improvers
  • Viscosity modifiers can be included in the lubricant compositions of this disclosure.
  • Viscosity modifiers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
  • Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters and viscosity modifier dispersants that function as both a viscosity modifier and a dispersant. Typical molecular weights of these polymers are between about 10,000 to 1,500,000, more typically about 20,000 to 1,200,000, and even more typically between about 50,000 and 1,000,000.
  • suitable viscosity modifiers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity modifier.
  • Another suitable viscosity modifier is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
  • Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
  • Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation“PARATONE®” (such as“PARATONE® 8921” and“PARATONE® 8941”); from Afton Chemical Corporation under the trade designation“Hi TEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation“Lubrizol® 7067C”.
  • Hydrogenated polyisoprene star polymers are commercially available from Infmeum International Limited, e.g., under the trade designation“SV200” and“SV600”.
  • Hydrogenated diene-styrene block copolymers are commercially available from Infmeum International Limited, e.g., under the trade designation“SV 50”.
  • the polymethacrylate or polyacrylate polymers can be linear polymers which are available from Evnoik Industries under the trade designation“Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation AstericTM (e.g., Lubrizol 87708 and Lubrizol 87725).
  • Viscoplex® e.g., Viscoplex 6-954
  • AstericTM e.g., Lubrizol 87708 and Lubrizol 87725.
  • Illustrative vinyl aromatic-containing polymers useful in this disclosure may be derived predominantly from vinyl aromatic hydrocarbon monomer.
  • Illustrative vinyl aromatic-containing copolymers useful in this disclosure may be represented by the following general formula:
  • viscosity modifiers may be used in an amount of less than about 10 weight percent, preferably less than about 7 weight percent, more preferably less than about 4 weight percent, and in certain instances, may be used at less than 2 weight percent, preferably less than about 1 weight percent, and more preferably less than about 0.5 weight percent, based on the total weight of the lubricating oil composition. Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil.
  • the viscosity modifier concentrations are given on an“as delivered” basis.
  • the active polymer is delivered with a diluent oil.
  • The“as delivered” viscosity modifier typically contains from 20 weight percent to 75 weight percent of an active polymer for polymethacrylate or polyacrylate polymers, or from 8 weight percent to 20 weight percent of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the“as delivered” polymer concentrate.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Patent Nos. 4,798,684 and 5,084,197, for example.
  • oxidation inhibitors Two general types of oxidation inhibitors are those that react with the initiators, peroxy radicals, and hydroperoxides to form inactive compounds, and those that decompose these materials to form less active compounds. Examples are hindered (alkylated) phenols, e.g. 6-di(tert- butyl)-4-methylphenol [2,6-di(tert-butyl)-p-cresol, DBPC], and aromatic amines, e.g. N-phenyl- . alpha. -naphthalamine. These are used in turbine, circulation, and hydraulic oils that are intended for extended service. [00177] Useful antioxidants include hindered phenols.
  • phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds.
  • Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other.
  • Typical phenolic antioxidants include the hindered phenols substituted with C6+ alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and
  • 2-methyl-6-t-butyl-4-dodecyl phenol may include for example hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure.
  • Examples of ortho-coupled phenols include: 2,2’-bis(4-heptyl-6-t-butyl-phenol); 2,2’-bis(4-octyl- 6-t-butyl-phenol); and 2,2’-bis(4-dodecyl-6-t-butyl-phenol).
  • Para-coupled bisphenols include for example 4,4’-bis(2,6-di-t-butyl phenol) and 4,4’-methylene-bis(2,6-di-t-butyl phenol).
  • phenol-based antioxidants include 2-t-butylphenol, 2-t-butyl-4- methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t- butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (manufactured by the Kawaguchi Kagaku Co.
  • Antage DBH 2,6-di-t-butylphenol and 2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4- ethylphenol; 2,6-di-t-butyl-4-alkoxyphenols such as 2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t- butyl-4-ethoxyphenol, 3,5-di-t-butyl-4-hydroxybenzylmercaptoocty- 1 acetate, alkyl-3-(3,5-di-t- butyl-4-hydroxyphenyl)propionates such as n-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by the Yoshitomi Seiyaku Co. under the trade designation "Yonox SS
  • Antage W-400 2,2'-methylenebis(4-ethyl-6-t-butylphenol)
  • Kawaguchi Kagaku Co. trade designation "Antage W-500”
  • bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butyl- phenol) (manufactured by the Kawaguchi Kagaku Co. under the trade designation "Antage W- 300")
  • 4,4'-methylenebis(2,6-di-t-butylphenol) manufactured by Laporte Performance Chemicals under the trade designation "Ionox 220AH”
  • phenol-based antioxidants include 4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane (Bisphenol A), 2,2-bis(3,5-di-t-butyl-4- hydroxyphenyl)propane, 4,4'-cyclohexylidenebis(2,6-di-t-butylphenol), hexamethylene glycol bis[3, (3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by the Ciba Speciality Chemicals Co.
  • the phenolic antioxidants include sulfurized and non-sulfurized phenolic antioxidants.
  • the terms“phenolic type” or“phenolic antioxidant” used herein include compounds having one or more than one hydroxyl group bound to an aromatic ring, which may itself be mononuclear, e.g., benzyl, or poly-nuclear, e.g., naphthyl and spiro aromatic compounds.
  • phenol type includes phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc., as well as alkyl or alkenyl and sulfurized alkyl or alkenyl derivatives thereof, and bisphenol type compounds including such bi-phenol compounds linked by alkylene bridges sulfuric bridges or oxygen bridges.
  • Alkyl phenols include mono- and poly-alkyl or alkenyl phenols, the alkyl or alkenyl group containing from 3-100 carbons, preferably 4 to 50 carbons and sulfurized derivatives thereof, the number of alkyl or alkenyl groups present in the aromatic ring ranging from 1 to up to the available unsatisfied valences of the aromatic ring remaining after counting the number of hydroxyl groups bound to the aromatic ring. [00181] Generally, therefore, the phenolic antioxidant may be represented by the general formula:
  • Ar is selected from the group consisting of:
  • R is a C3 - Cl 00 alkyl or alkenyl group, a sulfur substituted alkyl or alkenyl group, preferably a C4 - C50 alkyl or alkenyl group or sulfur substituted alkyl or alkenyl group, more preferably C3 - Cl 00 alkyl or sulfur substituted alkyl group, most preferably a C4 - C50 alkyl group
  • R G is a Cl - Cl 00 alkylene or sulfur substituted alkylene group, preferably a C2 - C50 alkylene or sulfur substituted alkylene group, more preferably a C2 - C20 alkylene or sulfur substituted alkylene group
  • y is at least 1 to up to the available valences of Ar
  • x ranges from 0 to up to the available valances of Ar-y
  • z ranges from 1 to 10
  • n ranges from 0 to 20
  • m is 0 to 4
  • p is 0 or
  • Preferred phenolic antioxidant compounds are the hindered phenolics and phenolic esters, which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other.
  • Typical phenolic antioxidants include the hindered phenols substituted with C1+ alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di- t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl phenol; and 2,6-di-t-butyl 4 alkoxy phenol; and
  • Phenolic type antioxidants are well known in the lubricating industry and commercial examples such as Ethanox® 4710, Irganox® 1076, Irganox® L1035, Irganox® 1010, Irganox® L109, Irganox® L118, Irganox® L135 and the like are familiar to those skilled in the art. The above is presented only by way of exemplification, not limitation on the type of phenolic antioxidants which can be used.
  • catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts ofb) one or more substituted N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c).
  • Catalytic antioxidants are more fully described in ET.S. Patent No. 8, 048,833, herein incorporated by reference in its entirety.
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula
  • R 8 is an aliphatic, aromatic or substituted aromatic group
  • R 9 is an aromatic or a substituted aromatic group
  • R 10 is H, alkyl, aryl or R u S(0)xR 12 where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Aromatic amine antioxidants include phenyl -a-naphthyl amine, which is described by the following molecular structure:
  • R z is hydrogen or a Cl - C14 linear or C3 - C14 branched alkyl group, preferably Cl - C10 linear or C3 - C10 branched alkyl group, more preferably linear or branched C6 - C8 and n is an integer ranging from 1 to 5 preferably 1.
  • a particular example is Irganox L06.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present disclosure include: p,p’- dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
  • amine-based antioxidants include dialkyldiphenylamines such as p,p'-dioctyldiphenylamine (manufactured by the Seiko Kagaku Co. under the trade designation "Nonflex OD-3"), p,p'-di-alpha-methylbenzyl- diphenylamine and N-p-butylphenyl-N-p'- octylphenylamine; monoalkyldiphenylamines such as mono-t-butyldiphenylamine, and monooctyldiphenylamine; bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine and di(2- ethyl-4-nonylphenyl)amine; alkylphenyl-l -naphthylamines such as octylphenyl-l-naphthylamine and N-t-do
  • a sulfur-containing antioxidant may be any and every antioxidant containing sulfur, for example, including dialkyl thiodipropionates such as dilauryl thiodipropionate and distearyl thiodipropionate, dialkyldithiocarbamic acid derivatives (excluding metal salts), bis(3,5-di-t-butyl- 4-hydroxybenzyl)sulfide, mercaptobenzothi azole, reaction products of phosphorus pentoxide and olefins, and dicetyl sulfide.
  • dialkyl thiodipropionates such as dilauryl thiodipropionate and distearyl thiodipropionate.
  • antioxidants examples include dialkylsulphides such as didodecylsulphide and dioctadecylsulphide; thiodipropionic acid esters such as didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate and dodecyloctadecyl thiodipropionate, and 2-mercaptobenzimidazole. Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
  • chlorinated aliphatic hydrocarbons such as chlorinated wax
  • organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene
  • phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate, phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecy
  • antioxidants which may be used in the lubricating oil compositions disclosed herein are oil-soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil. Examples of suitable copper antioxidants include copper dihydrocarbyl thio- or dithio-phosphates and copper salts of carboxylic acid (naturally occurring or synthetic). Other suitable copper salts include copper dithiacarbamates, sulphonates, phenates, and acetyl acetonates. Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are known to be particularly useful.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Although their presence is not required to obtain the benefit of this disclosure, antioxidant additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.1 to 3 weight percent, more preferably 0.1 to 2 weight percent, more preferably 0.1 to 1.5 weight percent. Pour Point Depressants (PPDs)
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • PPD additives may be used in an amount of zero to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
  • Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), polybutenyl succinic anhydride and sulfolane-type seal swell agents such as Lubrizol 730-type seal swell additives.
  • seal combatibility additives may be used in an amount of zero to 3 weight percent, preferably about 0.01 to 2 weight percent.
  • Antifoam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams.
  • Foam inhibitors include polymers of alkyl methacrylate especially useful poly alkyl acrylate polymers where alkyl is generally understood to be methyl, ethyl propyl, isopropyl, butyl, or iso butyl and polymers of dimethylsilicone which form materials called dimethylsiloxane polymers in the viscosity range of lOOcSt to l00,000cSt.
  • Other additives are defoamers, such as silicone polymers which have been post reacted with various carbon containing moieties, are the most widely used defoamers. Organic polymers are sometimes used as defoamers although much higher concentrations are required.
  • Antifoam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers. Although their presence is not required to obtain the benefit of this disclosure, usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
  • a demulsifier may advantageously be added to lubricant compositions.
  • the demulsifier is used to separate emulsions (e.g., water in oil).
  • An illustrative demulsifying component is described in EP-A-330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reaction of a bis-epoxide with a polyhydric alcohol.
  • Demulsifiers are commercially available and may be used in conventional minor amounts along with other additives such as antifoam agents. Although their presence is not required to obtain the benefit of this disclosure, usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
  • Demulsifying agents include alkoxylated phenols and phenol-formaldehyde resins and synthetic alkylaryl sulfonates such as metallic dinonylnaphthalene sulfonates.
  • a demulsifmg agent is a predominant amount of a water-soluble polyoxyalkylene glycol having a pre-selected molecular weight of any value in the range of between about 450 and 5000 or more.
  • An especially preferred family of water soluble polyoxyalkylene glycol useful in the compositions of the present disclosure may also be one produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product.
  • Polyoxyalkylene glycols useful in the present disclosure may be produced by a well- known process for preparing polyalkylene oxide having hydroxyl end-groups by subjecting an alcohol or a glycol ether and one or more alkylene oxide monomers such as ethylene oxide, butylene oxide, or propylene oxide to form block copolymers in addition polymerization while employing a strong base such as potassium hydroxide as a catalyst.
  • the polymerization is commonly carried out under a catalytic concentration of 0.3 to 1.0% by mole of potassium hydroxide to the monomer(s) and at high temperature, as l00°C to l60°C. It is well known fact that the potassium hydroxide being a catalyst is for the most part bonded to the chain- end of the produced polyalkylene oxide in a form of alkoxide in the polymer solution so obtained.
  • An especially preferred family of soluble polyoxyalkylene glycol useful in the compositions of the present disclosure may also be one produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water, air or other contaminants. A wide variety of these are commercially available.
  • antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Although their presence is not required to obtain the benefit of this disclosure, inhibitors and antirust additives may be used in an amount from zero to about 5 weight percent, preferably from 0.01 to about 1.5 weight percent.
  • Antirust additives include (short-chain) alkenyl succinic acids, partial esters thereof and nitrogen-containing derivatives thereof; and synthetic alkaryl sulfonates, such as metal dinonylnaphthalene sulfonates.
  • Anti-rust agents include, for example, monocarboxylic acids which have from 8 to 30 carbon atoms, alkyl or alkenyl succinates or partial esters thereof, hydroxy -fatty acids which have from 12 to 30 carbon atoms and derivatives thereof, sarcosines which have from 8 to 24 carbon atoms and derivatives thereof, amino acids and derivatives thereof, naphthenic acid and derivatives thereof, lanolin fatty acid, mercapto-fatty acids and paraffin oxides.
  • Examples of monocarboxylic acids include, for example, caprylic acid, pelargonic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, cerotic acid, montanic acid, melissic acid, oleic acid, docosanic acid, erucic acid, eicosenic acid, beef tallow fatty acid, soy bean fatty acid, coconut oil fatty acid, linolic acid, linoleic acid, tall oil fatty acid, l2-hydroxystearic acid, laurylsarcosinic acid, myritsylsarcosinic acid, palmitylsarcosinic acid, stearylsarcosinic acid, oleylsarcosinic acid, alkylated (C8-C20) phenoxyacetic acids, lanolin
  • polybasic carboxylic acids include, for example, the alkenyl (C 10-000) succinic acids indicated in CAS No. 27859-58-1 and ester derivatives thereof, dimer acid, N-acyl- N-alkyloxyalkyl aspartic acid esters (ET.S. Patent No. 5,275,749).
  • alkylamines which function as antirust additives or as reaction products with the above carboxylates to give amides and the like are represented by primary amines such as laurylamine, coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine, palmitylamine, n-heptadecylamine, stearylamine, n-nonadecylamine, n-eicosylamine, n- heneicosylamine, n-docosylamine, n-tricosylamine, n-pentacosylamine, oleylamine, beef tallow- amine, hydrogenated beef tallow-amine and soy bean-amine.
  • primary amines such as laurylamine, coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine, palmitylamine, n-heptadecylamine, ste
  • secondary amines examples include dilaurylamine, di-coconut-amine, di-n-tridecylamine, dimyristylamine, di-n- pentadecylamine, dipalmitylamine, di-n-pentadecylamine, distearylamine, di-n-nonadecylamine, di-n-eicosylamine, di-n-heneicosylamine, di-n-docosylamine, di-n-tricosylamine, di-n-pentacosyl- amine, dioleylamine, di-beef tallow-amine, di-hydrogenated beef tallow-amine and di-soy bean- amine.
  • N-alkylpolyalkyenediamines examples include:ethylenediamines such as laurylethylenediamine, coconut ethylenediamine, n- tridecylethylenediamine- , myristylethylenediamine, n-pentadecylethylenediamine, palmitylethylenediamine, n-heptadecylethylenediamine, stearylethylenediamine, n- nonadecylethylenediamine, n-eicosylethylenediamine, n-heneicosylethylenediamine, n- docosylethylendiamine, n-tricosylethylenediamine, n-pentacosylethylenediamine, oleylethylenediamine, beef tallow-ethylenediamine, hydrogenated beef tallow-ethylenediamine and soy bean-ethylenediamine; propylenediamines such as laurylpropylenediamine, coconut ethylenediamine, n
  • This type of component includes 2,5-dimercapto-l,3,4-thiadiazoles and derivatives thereof, mercaptobenzothiazoles, alkyltriazoles and benzotriazoles.
  • dibasic acids useful as anti-corrosion agents are adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid, l,lO-decanedicarboxylic acid, and fumaric acid.
  • the anti-corrosion combination is a straight or branch-chained, saturated or unsaturated monocarboxylic acid or ester thereof which may optionally be sulphurised in an amount up to 35% by weight.
  • the acid is a C4 to C22 straight chain unsaturated monocarboxylic acid.
  • the monocarboxylic acid may be a sulphurised oleic acid.
  • other suitable materials are oleic acid itself; valeric acid and erucic acid.
  • a component of the anti-corrosion combination is a triazole as previously defined.
  • a preferred triazole is tolylotri azole which may be included in the compositions of the disclosure include triazoles, thiazoles and certain diamine compounds which are useful as metal deactivators or metal passivators. Examples include triazole, benzotriazole and substituted benzotri azoles such as alkyl substituted derivatives.
  • the alkyl substituent generally contains up to 1.5 carbon atoms, preferably up to 8 carbon atoms.
  • the triazoles may contain other substituents on the aromatic ring such as halogens, nitro, amino, mercapto, etc.
  • Suitable compounds are benzotriazole and the tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles, octylbenzotriazoles, chlorobenzotriazoles and nitrobenzotriazoles. Benzotriazole and tolyltriazole are particularly preferred.
  • Illustrative substituents include, for example, alkyl that is straight or branched chain, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n- octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n- eicosyl; alkenyl that is straight or branched chain, for example, prop-2-enyl, but-2-enyl, 2-methyl- prop-2-enyl, pent-2-enyl, hexa-2,4-dienyl, dec-lO-enyl or eicos-2
  • Illustrative arylene moieties include, for example, phenylene and naphthylene.
  • the metal deactivating agents which can be used in the lubricating oil include, for example, benzotriazole and the 4-alkylbenzotriazoles such as 4-methylbenzotriazole and 4- ethylbenzotriazole; 5-alkylbenzotriazoles such as 5-methylbenzotriazole, 5-ethylbenzotriazole; 1- alkylbenzotriazoles such as l-dioctylauainomethyl-2,3-benzotriazole; benzotriazole derivatives such as the l-alkyltolutriazoles, for example, l-dioctylaminomethyl-2,3-t- olutriazole; benzimidazole and benzimidazole derivatives such as 2-(alkyldithio)-benzimidazoles, for example, such as 2-(octyldithio)-benzimidazole, 2-(decyldithio)benzimid
  • 1.3.4-thiadiazoles such as 2,5-bis(N,N-diethyldithiocarbamyl)-l,3,- 4-thiadiazole, 2,5-bis(N,N- dibutyldithiocarbamyl)-l, 3,4-thiadiazole and 2, 5-bis(N,N-dioctyldithiocarbamyl)l, 3,4- thiadiazole; thiadiazole derivatives of 2-N,N-dialkyldithiocarbamyl-5-mercapto-l,3,4-thiadiazoles such as 2-N,N-dibutyldithiocarbamyl-5-mercapto-l, 3, 4-thiadiazole and 2-N,N-dioctyl- dithiocarbamyl-5-mercapto-l, 3, 4-thiadiazole, and triazole derivatives of 1 -alkyl-2, 4-triazoles such as l-dioctylamino
  • metal deactivators and corrosion inhibitor additives may be present from zero to about 1% by weight, preferably from 0.01% to about 0.5% of the total lubricating oil composition.
  • a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
  • At least one friction modifier in a formulated lubricant can correspond to a friction modifier additive including a metal salt of a Group VI metal, such as a molybdenum-containing metal salt and/or tungsten-containing metal salt.
  • the friction modifier additive including the Group VI metal can have a free energy of adsorption (AG) on an oxygenated diamond-like carbon surface of -25 kJ/mol or less, or -28 kJ/mol or less, or -30 kJ/mol or less.
  • Some illustrative friction modifiers that include a Group VI metal may include, for example, organometallic compounds or materials, or mixtures thereof.
  • Illustrative organometallic friction modifiers useful in the lubricating oil formulations of this disclosure include, for example, molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Similar tungsten based compounds may be preferable.
  • Other friction modifiers that include a Group VI metal can include salts based on a cation including Group VI metal and sulfur.
  • Examples of the Group VI metal and sulfur-containing cation can include, but are not limited to, M03S4 and M03S7.
  • a formulated lubricant may contain other friction modifiers.
  • Other illustrative friction modifiers can include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.
  • Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.
  • Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like.
  • These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.
  • Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerol mono-stearate, and the like. These can include polyol esters, hydroxyl -containing polyol esters, and the like.
  • Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol mono-sterate, and the like.
  • glycerol polyols these can include trimethylolpropane, pentaerythritol, sorbitan, and the like.
  • esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters.
  • Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like.
  • the glycerol esters can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol can be preferred.
  • Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers.
  • the underlying alcohol portion can preferably be stearyl, myristyl, Cl 1 - C13 hydrocarbon, oleyl, isosteryl, and the like.
  • a list of other friction modifiers suitable for disclosure includes: (i) fatty phosphonates; (ii) fatty acid amides; (iii) fatty epoxides; (iv) borated fatty epoxides; (v) fatty amines; (vi) glycerol esters; (vii) borated glycerol esters; (viii) alkoxylated fatty amines; (ix) borated alkoxylated fatty amines; (x) metal salts of fatty acids; (xi) sulfurized olefins; (xii) condensation products of carboxylic acids or equivalents and polyalkylene-polyamines; (xiii) metal salts of alkyl salicylates; (xiv) amine salts of alkylphosphoric acids; (xv) fatty esters; (xvi) condensation products of carboxylic acids or equivalents with polyols and mixtures thereof. [00225] Representatives of each of these
  • the term“R” is conventionally referred to as an alkyl group but may also be hydrogen. It is, of course, possible that the alkyl group is actually alkenyl and thus the terms“alkyl” and“alkylated,” as used herein, will embrace other than saturated alkyl groups within the component.
  • the component should have sufficient hydrocarbyl groups to render it substantially oleophilic. In some embodiments the hydrocarbyl groups are substantially un branched. Many suitable such components are available commercially and may be synthesized as described in U.S. Patent No. 4,752,416. In some embodiments the component contains 8 to 24 carbon atoms in each of R groups.
  • the component may be a fatty phosphite containing 12 to 22 carbon atoms in each of the fatty radicals, or 16 to 20 carbon atoms.
  • the fatty phosphite can be formed from oleyl groups, thus having 18 carbon atoms in each fatty radical.
  • borated fatty epoxides are known from Canadian Patent No. 1,188,704. These oil-soluble boron- containing compositions are prepared by reacting, at a temperature from 80°C to 250°C, boric acid or boron trioxide with at least one fatty epoxide having the formula:
  • each of R 1 , R 2 , R 3 and R 4 is hydrogen or an aliphatic radical, or any two thereof together with the epoxy carbon atom or atoms to which they are attached, form a cyclic radical.
  • the fatty epoxide preferably contains at least 8 carbon atoms.
  • the borated fatty epoxides can be characterized by the method for their preparation which involves the reaction of two materials.
  • Reagent A can be boron trioxide or any of the various forms of boric acid including metaboric acid (HBO2), orthoboric acid (H3BO3) and tetraboric acid (H2B4O7). Boric acid, and especially orthoboric acid, is preferred.
  • Reagent B can be at least one fatty epoxide having the above formula. In the formula, each of the R groups is most often hydrogen or an aliphatic radical with at least one being a hydrocarbyl or aliphatic radical containing at least 6 carbon atoms.
  • the molar ratio of reagent A to reagent B is generally 1 :0.25 to 1 :4. Ratios of 1 : 1 to 1 :3 are preferred, with about 1 :2 being an especially preferred ratio.
  • the borated fatty epoxides can be prepared by merely blending the two reagents and heating them at temperature of 80°C to 250°C, preferably l00°C to 200°C, for a period of time sufficient for reaction to take place. If desired, the reaction may be effected in the presence of a substantially inert, normally liquid organic diluent. During the reaction, water is evolved and may be removed by distillation.
  • Borated amines are generally known from U.S. Patent No. 4,622, 158.
  • Borated amine friction modifiers (including (ix) borated alkoxylated fatty amines) are conveniently prepared by the reaction of a boron compounds, as described above, with the corresponding amines.
  • the amine can be a simple fatty amine or hydroxy containing tertiary amines.
  • the borated amines can be prepared by adding the boron reactant, as described above, to an amine reactant and heating the resulting mixture at a 50°C to 300°C, preferably l00°C to 250°C or l30°C to l80°C, with stirring. The reaction is continued until by-product water ceases to evolve from the reaction mixture indicating completion of the reaction.
  • ETHOMEENTM C/12 bis[2- hydroxyethyl]-coco-amine
  • ETHOMEENTM C/20 polyoxyethylene[lO]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 polyoxyethylene[l5]octadecylamine
  • Fatty amines and ethoxylated fatty amines are also described in ET.S. Patent No. 4,741,848.
  • Dihydroxyethyl tallowamine (commercially sold as ENT- 12TM) is included in these types of amines.
  • alkoxylated fatty amines and (v) fatty amines themselves (such as oleylamine and dihydroxyethyl tallowamine) are generally useful as friction modifiers in this disclosure. Such amines are commercially available.
  • Both borated and unborated fatty acid esters of glycerol can be used as friction modifiers.
  • the (vii) borated fatty acid esters of glycerol are prepared by borating a fatty acid ester of glycerol with boric acid with removal of the water of reaction.
  • there is sufficient boron present such that each boron will react with from 1.5 to 2.5 hydroxyl groups present in the reaction mixture.
  • the reaction may be carried out at a temperature in the range of 60°C to l35°C, in the absence or presence of any suitable organic solvent such as methanol, benzene, xylenes, toluene, or oil.
  • the (vi) fatty acid esters of glycerol themselves 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 are preferably prepared from C8 to C22 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 preferred, although, mixtures of mono- and diesters may be used.
  • commercial glycerol monooleate may contain a mixture of 45% to 55% by weight monoester and 55% to 45% diester.
  • Fatty acids can be used in preparing the above glycerol esters; they can also be used in preparing their (x) metal salts, (ii) amides, and (xii) imidazolines, any of which can also be used as friction modifiers.
  • Preferred fatty acids are those containing 10 to 24 carbon atoms, or 12 to 18.
  • the acids can be branched or straight-chain, saturated or unsaturated. In some embodiments the acids are straight-chain acids. In other embodiments the acids are branched.
  • Suitable acids include 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, coconut oil and Neat’s foot oil.
  • a particularly preferred acid is oleic acid.
  • Preferred metal salts include zinc and calcium salts. Examples are overbased calcium salts and basic oleic acid-zinc salt complexes, such as zinc oleate, which can be represented by the general formula Z OleateeOi.
  • Preferred amides are those prepared by condensation with ammonia or with primary or secondary amines such as ethylamine and diethanolamine.
  • Fatty imidazolines are the cyclic condensation product of an acid with a diamine or polyamine such as a poly ethylenepoly amine.
  • the imidazolines are generally represented by the structure:
  • the condensation products of carboxylic acids and polyalkyleneamines (xiii) may generally be imidazolines or amides. They may be derived from any of the carboxylic acids described above and any of the polyamines described herein.
  • Sulfurized olefins (xi) are well known commercial materials used as friction modifiers.
  • a particularly preferred sulfurized olefin is one which is prepared in accordance with the detailed teachings of U.S. Patent Nos. 4,957,651 and 4,959, 168. Described therein is a co-sulfurized 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 is preferably an aliphatic olefin, which usually will contain 4 to 40 carbon atoms, preferably from 8 to 36 carbon atoms. Terminal olefins, or alpha-olefins, are preferred, especially those having from 12 to 20 carbon atoms. Mixtures of these olefins are commercially available, and such mixtures are contemplated for use in this disclosure.
  • the co-sulfurized mixture of two or more of the reactants is prepared by reacting the mixture of appropriate reactants with a source of sulfur.
  • the mixture to be sulfurized can contain 10 to 90 parts of Reactant (1), or 0.1 to 15 parts by weight of Reactant (2); or 10 to 90 parts, often 15 to 60 parts, more often 25 to 35 parts by weight of Reactant (3), or 10 to 90 parts by weight of reactant (4).
  • the mixture in the present disclosure, includes Reactant (3) and at least one other member of the group of reactants identified as reactants (1), (2) and (4).
  • the sulfurization reaction generally is effected at an elevated temperature with agitation and optionally in an inert atmosphere and in the presence of an inert solvent.
  • the sulfurizing agents useful in the process of the present disclosure include elemental sulfur, which is preferred, hydrogen sulfide, sulfur halide plus sodium sulfide, and a mixture of hydrogen sulfide and sulfur or sulfur dioxide. Typically often 0.5 to 3 moles of sulfur are employed per mole of olefmic bonds. Sulfurized olefins may also include sulfurized oils such as vegetable oil, lard oil, oleic acid and olefin mixtures.
  • Metal salts of alkyl salicylates include calcium and other salts of long chain (e.g. C12 to C16) alkyl-substituted salicylic acids.
  • Amine salts of alkylphosphoric acids include salts of oleyl and other long chain esters of phosphoric acid, with amines as described below.
  • Useful amines in this regard are tertiary-aliphatic primary amines, sold under the tradename PrimeneTM.
  • the friction modifier is a fatty acid or fatty oil, a metal salt of a fatty acid, a fatty amide, a sulfurized fatty oil or fatty acid, an alkyl phosphate, an alkyl phosphate amine salt; a condensation product of a carboxylic acid and a polyamine, a borated fatty epoxide, a fatty imidazoline, or combinations thereof.
  • the friction modifier may be the condensation product of isostearic acid and tetraethylene pentamine, the condensation product of isostearic acid and 1- [tris(hydroxymethyl)]methylamine, borated polytetradecyloxirane, zinc oleate, hydroxylethyl-2- heptadecenyl imidazoline, di oleyl hydrogen phosphate, C14 - C18 alkyl phosphate or the amine salt thereof, sulfurized vegetable oil, sulfurized lard oil, sulfurized oleic acid, sulfurized olefins, oleyl amide, glycerol monooleate, soybean oil, or mixtures thereof.
  • the friction modifier may be glycerol monooleate, oleylamide, the reaction product of isostearic acid and 2-amino-2-hydroxymethyl-l, 3 -propanediol, sorbitan monooleate, 9-octadecenoic acid, isostearyl amide, isostearyl monooleate or combinations thereof.
  • friction modifiers tend to also act as emulsifiers. This is often due to the fact that friction modifiers often have non-polar fatty tails and polar head groups. Emulsibility, or rather decreased demulsibility, is a result that is undesirable in hydraulic fluids, where it is desirable for such compositions to remain separate from and not entrain any water with which the fluid may come into contact.
  • the friction modifiers of the present disclosure may be used to improve the antiwear performance of the hydraulic fluid, however in some embodiments care must be taken to avoid using the friction modifier at a level that would negatively impact the demulsibility of the fluid.
  • the lubricating oils of this disclosure exhibit desired properties, e.g., wear control, in the presence or absence of a friction modifier.
  • Illustrative boron-containing compounds useful in this disclosure include, for example, a borate ester, a boric acid, other boron compounds such as a boron oxide.
  • the boron compound is hydrolytically stable and is utilized for improved antiwear, and performs as a rust and corrosion inhibitor for copper bearings and other metal engine components.
  • the borated ester compound acts as an inhibitor for corrosion of metal to prevent corrosion of either ferrous or non-ferrous metals (e.g. copper, bronze, brass, titanium, aluminum and the like) or both, present in concentrations in which they are effective in inhibiting corrosion.
  • Patents describing techniques for making basic salts of sulfonic, carboxylic acids and mixtures thereof include U.S. Patent Nos. 5,354,485; 2,501,731; 2,616,911; 2,777,874; 3,384,585; 3,320,162; 3,488,284; and 3,629, 109. The disclosures of these patents are hereby incorporated by reference. Methods of preparing borated overbased compositions are found in U.S. Patent Nos. 4,744,920; 4,792,410; and PCT publication WO 88/03144. The disclosures of these references are hereby incorporated by reference.
  • the oil-soluble neutral or basic salts of alkali or alkaline earth metals salts may also be reacted with a boron compound.
  • An illustrative borate ester utilized in this disclosure is manufactured by Exxon-Mobil USA under the product designation of ("MCP 1286”) and MOBIL ADC700. Test data show the viscosity at l00°C using the D-445 method is 2.9 cSt; the viscosity at 40°C using the D-445 method is 11.9; the flash point using the D-93 method is 146; the pour point using the D-97 method is -69; and the percent boron as determined by the ICP method is 5.3%.
  • the borated ester (VanlubeTM 289), which is marketed as an antiwear/antiscuff additive and friction reducer, is a preferred borate ester useful in this disclosure.
  • An illustrative borate ester useful in this disclosure is the reaction product obtained by reacting about 1 mole fatty oil, about 1.0 to 2.5 moles diethanolamine followed by subsequent reaction with boric acid to yield about 0.1 to 3 percent boron by mass. It is believed that the reaction products may include one or both of the following two primary components, with the further listed components being possible components when the reaction is pushed toward full hydration:
  • Y represents a fatty oil residue.
  • the preferred fatty oils are glyceryl esters of higher fatty acids containing at least 12 carbon atoms and may contain 22 carbon atoms and higher. Such esters are commonly known as vegetable and animal oils. Vegetable oils particularly useful are oils derived from coconut, com, cottonseed, linseed, peanut, soybean and sunflower seed. Similarly, animal fatty oils such as tallow may be used.
  • the source of boron is boric acid or materials that afford boron and are capable of reacting with the intermediate reaction product of fatty oil and diethanolamine to form a borate ester composition.
  • organoborate ester composition is specifically discussed above, it should be understood that other organoborate ester compositions should also function with similar effect in the present disclosure, such as those set forth in U.S. Patent Application Publication No. 2003/0119682, which is incorporated herein by reference.
  • dispersions of borate salts such as potassium borate, may also be useful.
  • boron- containing compounds may be used up from zero to 10.0% percent, more preferably from about 0.01% to about 5%, and most preferably from about 0.1% to about 3.0 %.
  • An effective elemental boron range of up to 1000 ppm or less than 1% elemental boron.
  • a preferred concentration of elemental boron is from 100 to 1000 ppm and more preferably from 100 to 300 ppm.
  • Typical amounts of such additives useful in the present disclosure are shown in Table 3 below.
  • Antifoam Agent 0.001-3 0.001-0.3
  • Demulsifier 0.001-3 0.001-0.15
  • Viscosity Modifier (solid 0 1-2 0 1-1
  • additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
  • Example 1 Variation in Oxygen Content with Depth for Oxygenated Diamond-Like Carbon
  • a sample of borated diamond-like carbon was analyzed using X-ray photoelectron spectroscopy (XPS) to determine elemental composition.
  • XPS X-ray photoelectron spectroscopy
  • the surface of the sample was sputtered with an argon ion (Ar+) beam. Based on the sputtering rate, each 6 seconds corresponds to a drilling depth of 1 nm. At various depths the sample was analyzed to generate plots of elemental concentration versus depth into the sample.
  • FIG. 1 shows the relative concentration of oxygen plotted against the sputtering time for the sample.
  • FIG. 2 shows a similar concentration profile versus sputtering time for carbon. As shown in FIG. 1, the intensity of oxygen is highest at the initial surface of the sample prior to any sputtering, but rapidly drops off so that the oxygen concentration is substantially lower for the measurement performed after the first six second time period. By contrast, in FIG. 2 the carbon concentration increases modestly after the initial sputtering time period and then generally remains at the higher level. Based on the measured XPS intensities, an initial oxygen to carbon ratio was calculated for the surface of the borated diamond-like carbon sample prior to sputtering and after the first six second time period.
  • the oxygen to carbon ratio prior to any sputtering was calculated as roughly 1 : 9. After sputtering to remove the top 1 nm of the layer, the oxygen to carbon ratio dropped to roughly 1 : 30.
  • the ratio of boron to carbon was also determined using XPS on the sample at the various levels of sputtering. The boron to carbon ratio in the borated sample remained relatively constant at a value of roughly 1 : 14 or 1 : 15.
  • a non-borated oxygenated diamond-like carbon surface was characterized using XPS with argon ion sputtering. Based on the XPS measurements, the surface of the non-borated diamond-like carbon sample had an oxygen to carbon ratio of roughly 1 : 13. This result may indicate that the presence of boron in the diamond-like carbon layer facilitated incorporation of additional oxygen at the surface of the layer.
  • the sp 2 /sp 3 ratio of the DLC based on XPS analysis was roughly 1 : 1.
  • Adsorption isotherms were determined according to the method described herein for Mo-containing friction modifiers on various surfaces. As explained above, this included using a quartz crystal microbalance apparatus to determine mass adsorption for various friction modifiers in lubricating oils at a series of concentrations.
  • adsorption values are shown corresponding to amount of mass adsorbed relative to mole fraction of Mo in a lubricant exposed to a surface for Adeka Sakura Lube 300 - molybdenum dithiophosphate (MoDTP).
  • the adsorption values shown in FIG. 3 correspond to adsorption on an iron oxide surface, a borated and oxygenated diamond-like carbon surface, and a non-borated oxygenated diamond-like carbon surface.
  • the iron oxide surfaces in this and other examples corresponded to a surface of Fe30 4 (magnetite).
  • the DLC surfaces had a sp 2 /sp 3 ratio based on XPS analysis of roughly 1 : 1.
  • FIG. 3 also shows curve fits representing adsorption isotherms for adsorption on the iron oxide surface (curve 315) and the borated and oxygenated diamond-like carbon surface (curve 325). Such a curve fit can also be used to determine the free energy of adsorption, as described above.
  • FIG. 4 shows adsorption values for an Infmeum C9455B Mo-trimer compound on an iron oxide surface and a borated and oxygenated diamond-like carbon surface.
  • FIG. 4 also shows a curve fit representing an adsorption isotherm for adsorption on the borated and oxygenated diamond-like carbon surface (curve 425).
  • FIG. 5 shows adsorption values for Adeka Sakura Lube 515 molybdenum dithiocarbamate (MoDTC) on an iron oxide surface (data points 510), a borated and oxygenated diamond-like carbon surface (data points 520), a non-borated oxygenated diamond-like carbon surface (data points 530), and a polytetrafluoroethylene surface (PTFE, data points 540).
  • FIG. 5 also shows a curve fit representing an adsorption isotherm for adsorption on the borated and oxygenated diamond-like carbon surface (curve 525).
  • FIG. 9 shows adsorption values for an Mo3S 4 -based friction modifier (corresponding to Mo3S 4 [(2-ethylhexyl)2dtc] 4 ) on an iron oxide surface (data points 910) and a borated and oxygenated diamond-like carbon surface (data points 920).
  • FIG. 9 also shows curve fits representing adsorption isotherms for the iron oxide surface (curve 915) and the borated and oxygenated diamond-like carbon surface (curve 925).
  • the MoDTP friction modifier has a free energy of adsorption of less than -25 kJ/mol for all of the surfaces investigated.
  • the free energy of adsorption (AG) is somewhat lower on the diamond-like carbon surfaces.
  • the free energy of adsorption is -31 kJ/mol on the iron oxide surface; is -35 kJ/mol on the non-borated DLC surface, and -35 kJ/mol on the borated DLC surface.
  • the data in FIG. 4 shows similarly favorable adsorption values for the Mo-trimer (M03S7) compound, with a free energy of adsorption of -32 kJ/mol on both the iron oxide and the borated DLC surfaces.
  • the data in FIG. 9 for the M03S4- based friction modifier also resulted in a free energy of adsorption of -32 kJ/mol on the borated DLC surface.
  • FIG. 5 shows different adsorption behavior. Based on the data in FIG. 5, the resulting free energy of adsorption for MoDTC on both the borated and non-borated surfaces was only -24.6 kJ/mol. The free energy of adsorption was still higher on the iron oxide surface (- 21.2 kJ/mol) and the PTFE surface.
  • BDLC refers to the borated (and oxygenated) diamond-like carbon surface
  • n-BDLC refers to the non-borated (but still oxygenated) surface.
  • Table 4 also shows the final surface coverage for the various friction modifiers at saturation.
  • FIG. 6 shows the friction coefficient and wear depth measured for each friction modifier at a concentration corresponding with 700 wppm molybdenum, along with the friction coefficient and wear depth for the engine oil without an added friction modifier.
  • addition of MoDTC resulted in a reduction in the friction coefficient at the diamond-like carbon surface, but with an accompanying substantial increase in wear depth on the diamond-like carbon surface relative to the engine oil without an added friction modifier.
  • the Cis thiol did not result in increased wear, but also did not result in a substantial reduction in the friction coefficient.
  • the Mo-containing friction modifiers with free energies of adsorption on DLC of less than -25 kJ/mol all resulted in a substantial reduction in friction coefficient while also unexpectedly reducing the wear depth on the diamond-like carbon surface.
  • FIG. 6 The results in FIG. 6 can be further illustrated by plotting the friction coefficient and wear depth results versus the free energy of adsorption for the various friction modifiers.
  • FIG. 7 shows the results from FIG. 6, but replotted versus the AG value associated with each friction modifier on the borated and oxygenated diamond-like carbon surface. As shown in FIG. 7, the AG value of the friction modifier does not appear to impact the friction coefficient. However, the AG value appears to be correlated with the resulting wear depth associated with use of the friction modifier. It is noted that the Cis thiol from FIG. 6 is not included in the plot shown in FIG. 7.
  • FIG. 8 provides an illustration of the relationship between Mo content in a lubricant, friction coefficient, and wear depth. In FIG. 8, results are shown from additional ring and block tests with different concentrations of the Mo-containing friction modifiers in the engine oil formulation.
  • Mo concentrations of up to 750 wppm or possibly higher can be used while maintaining a wear depth that is less than the sample depth of 1.2 pm. As shown in FIG. 8, at Mo concentrations of 100 wppm or more, the Mo-trimer provides a substantially larger decrease in the friction coefficient (friction coefficient of 0.05 or less) while also unexpectedly reducing or minimizing the amount of wear depth.
  • the molecular diameter and polar site diameter for various friction modifiers was calculated using a commercially available molecular modeling tool.
  • Table 5 shows the molecular weight, molecular diameter, and polar diameter for the friction modifiers. The molecular diameters were calculated based on twice the molecular radius.
  • the molecular radius, R is defined as the average distance of all atoms in the molecule with respect to the configurational center of the molecule (not mass weighted).
  • the calculation for the polar site diameter, 2R P is similar, but only accounts for the polar atoms within the friction modifier. It is noted that the molecular diameter may be different from the time-averaged value, and may also depend on solvent effects. The polar site diameter is expected to have a lower variation with respect to such factors.
  • the configurations of the molecules were obtained from geometry optimization calcultions using Density Functional Theory (DFT). Details of the DFT calculations are given in Section 2.4 of the following publication on organo-metallic compounds: C.E.S. Bernardes et al., J. Phys. Chem. A, 2013, 117, 11107-11113. It is noted that the molecular diameter and polar site diameter for a C ix thiol friction modifier is expected to be similar to the values for stearic acid.
  • DFT Density Functional Theory
  • Table 5 shows the molecular weight, the molecular diameter, 2R, and the polar diameter, 2R P , for different Mo-containing friction modifiers.
  • MoDTC and MoDTP both contain 2-ethylhexyl side chains that are attached to the core structures; those structures (MoDTC and MoDTP) were taken from the following publication: Y. Yamamoto and S. Gondo, Tribology Transactions, 1989, 32, 251-257.
  • MoDTC has a smaller polar site diameter than the other Mo-containing friction modifiers in Table 5, even though the molecular diameter of MoDTC is similar to the molecular diameter for MoDTP.
  • the smaller polar site diameter of MoDTC may prevent MoDTC from fully bridging between oxygen sites on an oxygenated diamond-like carbon surface, which could reduce or minimize the likelihood of forming a substantially complete layer of MoDTC on the surface.
  • Embodiment 1 A method for lubricating a machine surface comprising: supplying a lubricant comprising a Group VI metal-containing friction modifier to a surface layer comprising diamond-like carbon with a surface oxygen to carbon ratio of 1 : 15 or more, the lubricant comprising 0.05 wt% to 0.2 wt% of the Group VI metal-containing friction modifier, the Group VI metal-containing friction modifier comprising a AG of adsorption on the diamond-like carbon of -25 kJ/mol or less (or -28 kJ/mol or less, or -30 kJ/mol or less).
  • Embodiment 2 The method of Embodiment 1, wherein the Group VI metal-containing friction modifier comprises a polar site diameter of 5.0 Angstroms or more (or 7.0 or more).
  • Embodiment 3 The method of any of the above embodiments, wherein the diamond like carbon comprises 15 mole% or more of hydrogen, or 20 mole% or more.
  • Embodiment 4 The method of any of the above embodiments, wherein the Group VI metal-containing friction modifier comprises an Mo-containing friction modifier.
  • Embodiment 5 The method of any of the above embodiments, wherein the lubricant comprises 50 wppm or more of Group VI metal, or 200 wppm or more, or 500 wppm or more, or 800 wppm or more; or wherein the lubricant comprises 100 wppm or more of Mo, or 300 wppm or more, or 500 wppm or more, or 800 wppm or more.
  • Embodiment 6 The method of any of the above embodiments, wherein the friction modifier comprises an Mo-containing friction modifier.
  • Embodiment 7 The method of any of the above embodiments, wherein the friction modifier comprises MoDTP, [Mo3S 4 ](dtc)2, a trinuclear molybdenum compound, or a combination thereof.
  • Embodiment 8 The method of any of the above embodiments, wherein the surface layer comprising diamond-like carbon comprises a layer depth of 2.0 pm or more of diamond-like carbon.
  • Embodiment 9 The method of any of the above embodiments, wherein the surface oxygen to carbon ratio is 1 : 10 or more.
  • Embodiment 10 The method of any of the above embodiments, wherein the surface oxygen to carbon ratio comprises a top 1.0 nm at the surface of the diamond-like carbon, or a top 0.7 nm.
  • Embodiment 11 The method of any of the above embodiments, wherein the lubricant further comprises a friction coefficient of 0.06 or less, or 0.05 or less.
  • Embodiment 12 The method of any of the above embodiments, wherein the lubricant is supplied to a machine surface layer positioned in opposition to a steel surface layer.
  • Embodiment 13 The method of any of the above embodiments, wherein the diamond- like carbon comprises borated diamond-like carbon, the borated diamond-like carbon optionally having a boron to carbon ratio of 0.5 : 100 or more, or 1.0 : 100 or more.
  • Embodiment 14 The method of Embodiment 13, wherein the borated diamond-like carbon comprises an oxygen to carbon ratio of 1 : 10 or more in a surface portion having a depth of 1.0 nm, or in a surface portion having a depth of 0.7 nm, or in a surface portion having a depth of 0.5 nm.
  • Embodiment 15 The method of any of the above embodiments, wherein a ratio of sp 2 to sp 3 hybridized carbons in the diamond-like carbon is 0.5 to 2.5, or 0.7 to 1.5.

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

Abstract

L'invention concerne des procédés pour lubrifier des surfaces de carbone de type diamant oxygéné pour réduire le frottement tout en diminuant ou en réduisant au minimum l'usure sur la surface. Une couche de surface de carbone de type diamant présentant un rapport de surface d'oxygène à carbone de 1:15 ou plus peut être lubrifiée à l'aide d'une huile lubrifiante qui comprend un additif modificateur du frottement à base de molybdène, un additif modificateur du frottement à base de tungstène ou une combinaison correspondante. Le modificateur du frottement à base de Mo (et/ou un autre modificateur du frottement basé sur un métal du groupe VI) peut être sélectionné sur la base de l'énergie libre de Gibbs d'adsorption (AG) pour le modificateur du frottement sur une surface de carbone de type diamant oxygéné. L'utilisation d'un modificateur du frottement à base d'un métal du groupe VI présentant une AG d'adsorption d'une amplitude suffisamment grande peut réduire le frottement à la surface du carbone de type diamant oxygéné tout en provoquant une quantité diminuée ou réduite au minimum d'usure pendant la lubrification. drawing: Fig. 1 AA%%% Intensité BB%%% Durée de pulvérisation (min)
PCT/US2018/063575 2017-12-29 2018-12-03 Lubrification de surfaces de carbone de type diamant oxygéné WO2019133191A1 (fr)

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CN113670960A (zh) * 2021-07-23 2021-11-19 西南石油大学 一种基于分子模拟的真实页岩气吸附量预测方法

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