Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
• • 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
  • C10M137/08—Ammonium or amine 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
  • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles
• • 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
• • 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
  • C10M2223/043—Ammonium or amine salts thereof
• • 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
  • 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
  • C10M2223/047—Thioderivatives not containing metallic elements
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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
  • C10N2030/54—Fuel economy
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/02—Bearings
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

• the disclosed technology relates to a lubricant composition for automotive or industrial gears, as well as axles and bearings, the lubricant composition containing an oil of lubricating viscosity, a phosphate and/or thiophosphate compound, and a metal thiophosphate compound, such as zinc dialkyldithiophosphate, as well as a method of improving automotive or industrial gear operating efficiency and temperature by lubricating such automotive or industrial gears with the lubricant composition.
• Driveline power transmitting devices (such as gears or transmissions) present highly challenging technological problems and solutions for satisfying the multiple and often conflicting lubricating requirements, while providing durability and cleanliness.
• Improving operating efficiency is a common goal shared by both original equipment manufacturers and lubricant manufacturers.
• Original equipment manufacturers may focus on using mechanical processing methods to reduce surface roughness in an effort to improve operating efficiency. These mechanical processing methods include honing, top polishing, and vibratory finishing.
• lubricant manufacturers often target optimizing viscosity and lowering fluid traction coefficients in their efforts to optimize operating efficiency.
• Current mechanical processing methods can be expensive and time consuming to implement for large scale automotive gear production. Therefore, there is a desire to improve operating efficiency by modifying fluid properties, instead of relying on mechanical processes to achieve this goal.
• a lubricant solution that can reduce surface roughness, reduce the fluid traction coefficient and/or improve fluid efficiency would be technically and commercially beneficial.
• One aspect of the technology is directed to a lubricant composition
• a lubricant composition comprising an oil of lubricating viscosity, from 0.5 to 2.0 wt% of an amine alkyl(thio)phosphate compound, and from 0.1 to 2 wt%, or 0.2 to 1.9 wt%, or 0.3 to 1 wt% of a metal alkylthiophosphate.
• the amine alkyl(thio)phosphate can be simply an amine alkylphosphate. In other embodiments, the amine alkyl(thio)phosphate can be an amine alkylthiophosphate. In further embodiments, the amine alkyl(thio)phosphate can include a combination of both amine phosphate and amine alkylthiophosphate.
• the lubricant can include an amine phosphate that is a substantially sulfur-free alkyl phosphate amine salt having at least about 30 mole percent of the phosphorus atoms in an alkyl pyrophosphate salt structure.
• at least about 80 mole percent of the alkyl groups in such a sulfur-free alkyl phosphate can be secondary alkyl groups of about 3 to about 12 carbon atoms.
• at least about 25 mole percent of the alkyl groups in such a sulfur-free alkyl phosphate can be primary alkyl groups of about 3 to about 12 carbon atoms.
• the amine alkylthiophosphate can be a dialkyldithiophosphate.
• the metal alkylthiophosphate in the lubricant composition can include a zinc dialkyldithiophosphate.
• the zinc dialkyldithiophosphate can be a secondary zinc dialkyldithiophosphate.
• the lubricant composition can also contain other additives.
• the lubricant composition can include sulfur containing additives in an amount to provide the composition with a total sulfur level of about 1 to about 5 or about 2 to about 5 wt%.
• the lubricant composition can have a total phosphorus level of about 0.01 to about 0.5 wt%.
• Another aspect of the technology encompasses a method of lubricating a driveline device by supplying to the driveline device a lubricant composition as described, and operating the driveline device.
• the driveline device can be, for example, an axle, a bearing, a transmission or a gear.
• One aspect of the invention is a lubricant composition for a driveline device containing (a) an oil of lubricating viscosity, (b) at least one amine alkyl(thio)phosphate, and (b) a metal alkylthiophosphate.
• the base oil may be selected from any of the base oils in Groups I-V of the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011), namely Base Oil Category Sulfur (%) Saturates (%) Viscosity Index Group I >0.03 and/or ⁇ 90 80 to less than 120 Group II ⁇ 0.03 and ⁇ 90 80 to less than 120 Group III ⁇ 0.03 and ⁇ 90 ⁇ 120 Group IV All polyalphaolefins (PAOs) Group V All others not included in Groups I, II, III or IV
• Groups I, II and III are mineral oil base stocks. Other generally recognized categories of base oils may be used, even if not officially identified by the API: Group II+, referring to materials of Group II having a viscosity index of 110-119 and lower volatility than other Group II oils; and Group III+, referring to materials of Group III having a viscosity index greater than or equal to 130.
• the oil of lubricating viscosity can include natural or synthetic oils and mixtures thereof. Mixture of mineral oil and synthetic oils, e.g., polyalphaolefin oils and/or polyester oils, may be used.
• the oil of lubricating viscosity has a kinematic viscosity at 100 °C by ASTM D445 of 1.5 to 7.5, or 2 to 7, or 2.5 to 6.5, or 3 to 6 mm 2 /s. In one embodiment the oil of lubricating viscosity comprises a poly alpha olefin having a kinematic viscotiy at 100 °C by ASTM D445 of 1.5 to 7.5 or any of the other aforementioned ranges.
• the lubricant of the disclosed technology will include at least one amine alkyl(thio)phosphate.
• thio the inclusion of "thio" in the parenthesis means that the phosphate may or may not contain sulfur atoms.
• the amine alkyl(thio)phosphate can include an amine phosphate, that is, a phosphate that is substantially sulfur-free.
• substantially sulfur free it is meant that sulfur is not intentionally added to the amine phosphate, and preferably the amine phosphate is completely free of sulfur.
• sulfur contamination levels may be less than 2.5%, or 1%, 0.1%, or 0.01% by weight to be considered substantially sulfur free.
• the amine phosphate may include at least 30 mole percent of the phosphorus atoms in an alkyl pyrophosphate structure, as opposed to an orthophosphate (or monomeric phosphate) structure.
• the percentage of phosphorus atoms in the pyrophosphate structure may be 30 to 100 mole %, or 40 to 90 % or 50 to 80% or 55 to 70 % or 55 to 65%.
• the remaining amount of the phosphorus atoms may be in an orthophosphate structure or may consist, in part, in unreacted phosphorus acid or other phosphorus species.
• up to 60 or up to 50 mole percent of the phosphorus atoms are in mono- or di-alkyl-orthophosphate salt structure.
• the amine phosphate as present in the pyrophosphate form, may be represented in part by a half neutralized salt of formula (I) and/or a fully neutralized salt as in formula (II).
• a half neutralized salt of formula (I) and/or a fully neutralized salt as in formula (II).
• the extent of neutralization of the amine phosphate in practice may be 50% to 100%, or 80% to 99%, or 90% to 98%, or 93% to 97%, or about 95%.
• Variants of these materials may also be present, such as a variant of formula (I) or formula (II) wherein the -OH group (in (I) is replaced by another -OR 1 group or wherein one or more -OR 1 groups are replaced by -OH groups, or wherein an R 1 group is replaced by a phosphorus-containing group, that is, those comprising a third phosphorus structure in place of a terminal R 1 group.
• Illustrative variant structures may include the following:
• the pyrophosphate salts may be distinguished from orthophosphate salts of the general structure which optionally may also be present in amounts as indicated above.
• the amine phosphate may also include some amount of partial esters including mono- and diesters of the orthophosphate structure and diesters of the pyrophosphate structure.
• each R 1 is independently an alkyl group of 3 to 12 carbon atoms.
• the alkyl groups may be primary or secondary groups, or a mixture of both primary and secondary.
• at least 80 mole percent, or at least 85, 90, 95, or 99 percent, of the R 1 alkyl groups will be secondary alkyl groups.
• at least 25 mole percent, or at least 30, 40, 50, 60, 70, 80 or 90 or even 99 mole percent, of the R 1 alkyl groups will be primary alkyl groups.
• the alkyl groups will have 3 or 4 to 12 carbon atoms, or 3 to 8, or 4 to 6, or 5 to 10, or 6 to 8 carbon atoms.
• the alkyl groups can be straight chain, branched, cyclic or aromatic.
• Such groups include 2-butyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methyl-2-pentyl, and other such secondary groups and isomers thereof having 6, 7, 8, 9, 10, 11, or 12 carbon atoms as well as propyl, butyl, isobutyl, pentyl, 3-methylbutyl, 2-methylbutyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenethyl, and other such primary groups and isomers thereof having 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.
• the amine alkyl(thio)phosphate may also be an amine alkylthiophosphate, wherein the alkylthiophosphate is represented by the formula (R'O) 2 PSSH, wherein each R' is independently a hydrocarbyl group containing from about 3 to about 30, preferably from about 3 up to about 18, or from about 3 up to about 12, or from up to about 8 carbon atoms.
• Example R' groups can include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl, n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and tridecyl groups.
• Illustrative lower alkylphenyl R' groups include butylphenyl, amylphenyl, heptylphenyl, etc.
• mixtures of R' groups include: 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl and isooctyl.
• the alkylthiophosphate of the amine alkylthiophosphate may be reacted with an epoxide or a polyhydric alcohol, such as glycerol.
• This reaction product may be used alone, or further reacted with a phosphorus acid, anhydride, or lower ester.
• the epoxide is generally an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide, etc. Ethylene oxide and propylene oxide are preferred.
• the polyhydric alcohols are described above.
• the glycols may be aliphatic glycols having from 2 to about 12, or from about 2 to about 6, or from 2 or 3 carbon atoms.
• Glycols include ethylene glycol, propylene glycol, and the like.
• the alkylthiophosphate, glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same are described in U.S. Pat. Nos. 3,197,405 and 3,544,465 which are incorporated herein by reference for their disclosure to these.
• the amine component of the amine alkyl(thio)phosphate may be represented by R 2 3 NH, where each R 2 is independently hydrogen or a hydrocarbyl group or an ester-containing group, or an ether-containing group, provided that at least one R 2 group is a hydrocarbyl group or an ester-containing group or an ether-containing group (that is, not NH 3 ).
• Suitable hydrocarbyl amines include primary amines having 1 to 18 carbon atoms, or 3 to 12, or 4 to 10 carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and isomers thereof, pentylamine and isomers thereof, hexylamine and isomers thereof, heptylamine and isomers thereof, octylamine and isomers thereof such as isooctylamine and 2-ethylhexylamine, as well as higher amines.
• Other primary amines include dodecylamine, fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine.
• fatty amines include commercially available fatty amines such as "Armeen ® " amines (products available from Akzo Chemicals, Chicago, Ill.), such as Armeen ® C, Armeen ® O, Armeen ® OL, Armeen ® T, Armeen ® HT, Armeen ® S and Armeen ® SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
• Secondary amines that may be used include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethyl-amine, ethylbutylamine, bis-2-ethylhexylamine, N-methyl-1-amino-cyclohexane, Armeen ® 2C, and ethylamylamine.
• the secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
• Suitable tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine (Armeen ® DMOD). Triisodecylamine or tridecylamine and isomers thereof may be used.
• mixtures of amines include (i) an amine with 11 to 14 carbon atoms on tertiary alkyl primary groups, (ii) an amine with 14 to 18 carbon atoms on tertiary alkyl primary groups, or (iii) an amine with 18 to 22 carbon atoms on tertiary alkyl primary groups.
• tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine), tert-decylamine (such as 1,1-dimethyloctylamine), tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanyl-amine.
• a useful mixture of amines includes "Primene ® 81R” or “Primene ® JMT.”
• Primene ® 81R and Primene ® JMT may be mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines, respectively.
• the amine may be an ester-containing amine such as an N-hydrocarbyl-substituted ⁇ - or ⁇ -amino(thio)ester, which is therefore a secondary amine.
• the ester-containing amine may, for example, be prepared by Michael addition of a primary amine, typically having a branched hydrocarbyl group, with an ethylenically unsaturated ester or thio ester, or, for example, by reductive amination of the esters of 5-oxy substituted carboxylic acids or 5-oxy substituted thiocarboxylic acids.
• esters of 5-halogen substituted carboxylic acids or 5-halogen substituted thiocarboxylic acids may also be prepared by amination of the esters of 5-halogen substituted carboxylic acids or 5-halogen substituted thiocarboxylic acids, or by reductive amination of the esters of 2-amino substituted hexanedioic acids, or by alkylation of the esters of 2-aminohexanedioic acids.
• the amine of whatever type, will be reacted to neutralize the acidic group(s) on the phosphorus ester component, to prepare the amine alkyl(thio)phosphate.
• the amine alkyl(thio)phosphate may be a phosphate amine of formulas (I) or (II), or variants thereof, with the amine being 2-ethylhexylamine.
• the amine alkyl(thio)phosphate may be an amine phosphate of formulas (I) or (II), or variants thereof, with the amine being an N-hydrocarbyl-substituted ⁇ - or ⁇ -amino(thio)ester.
• the amine alkyl(thio)phosphate can be an amine alkylthiophosphate that is the reaction product of a C 14 to C 18 alkylated dialkyldithiophosphoric acid with Primene 81R TM (produced and sold by Rohm & Haas) which is a mixture of C 11 to C 14 tertiary alkyl primary amines.
• the amine alkyl(thio)phosphate can include combinations of amine phosphates, combinations of amine alkylthiophosphates, and combinations of amine phosphates with amine alkylthiophosphates.
• the amount of amine alkyl(thio)phosphate in the lubricant composition may be 0.01 to 5 percent by weight.
• Alternative amounts of the amine alkyl(thio)phosphate may be 0.2 to 3 percent, or 0.2 to 1.2 percent, or 0.5 to 2.0 percent, or 0.55 to 1.4 percent, or 0.6 to 1.3 percent, or 0.7 to 1.2, or 1 to 2, or even 1.5 to 2, or 1.2 to 1.8 percent by weight or even from 1.8 to 2.2 percent by weight.
• the amount may be suitable to provide phosphorus to the lubricant formulation in an amount of 200 to 3000 parts per million by weight (ppm), or 400 to 2000 ppm, or 300 to 2000, or 600 to 1500 ppm, or 700 to 1100 ppm, or 900 to 1900, or 1100 to 1800 ppm, or 1200 to 1600 ppm or 1500 to 2000 ppm.
• ppm parts per million by weight
• amine alkyl(thio)phosphate will typically comprise a mixture of various individual chemical species.
• Reference herein to an amine alkyl(thio)phosphate will be understood by those of ordinary skill to encompass mixtures of such compounds as may be prepared by the described syntheses.
• the lubricant composition will further include a metal alkylthiophosphate compound.
• the metal alkylthiophosphate compound can be represented by the formula: wherein R 25 and R 26 are independently hydrogen, hydrocarbyl groups or mixtures thereof, provided that at least one of R 25 and R 26 is a hydrocarbyl group, preferably an alkyl or cycloalkyl with 1 to 30, or 2 to 20 and in some cases 2 to 15 carbon atoms.
• R 25 and R 26 can be secondary alkyl groups of 2 to 8 carbon atoms, or even from 3 to 6 carbon atoms, such as, for example, those derived from 4-methylpentan-2-ol or isopropanol.
• M is a metal, and n is an integer equal to the available valence of M.
• M is mono- or di- or trivalent, preferably divalent, more preferably a divalent transition metal, and most preferably zinc.
• metal alkylthiophosphates include zinc isopropyl methyl-amyl dithiophosphate, zinc isopropyl isooctyl dithiophosphate, zinc di(cyclohexyl)dithiophosphate, zinc isobutyl 2-ethylhexyl dithiophosphate, zinc isopropyl 2-ethylhexyl dithiophosphate, zinc isobutyl isoamyl dithiophosphate, zinc isopropyl n-butyl dithiophosphate, calcium di(hexyl)dithiophosphate, barium di(nonyl)dithiophosphate, zinc di(isobutyl) dithiophosphate, zinc isopropyl secondary-butyl dithiophosphate, zinc isopropyl dithiophosphate, zinc isopropyl 4-methylpentan-2-ol dithiophosphate, zinc 4-methylpentan-2-ol dithiophosphate or
• the metal alkylthiophosphate may be a zinc dialkyldithiophosphate.
• Zinc dialkyldithiophosphates may be described as primary zinc dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in its preparation.
• the lubricant composition can include a primary zinc dialkyldithiophosphate.
• the lubricant composition can include a secondary zinc dialkyldithiophosphate.
• the lubricant composition can include a mixture of primary and secondary zinc dialkyldithiophosphates.
• Metal from the metal alkylthiophosphate such as zinc, may be supplied at a concentration of from about 0.02 to about 0.095 wt% zinc, or from about 0.025 to 0.085 wt%, or even from about 0.03 to about 0.075 wt% zinc. Such levels may be associated with a metal alkylthiophosphate concentration of from about 0.2 to about 0.8 wt%, of from about 0.25 to 0.75 wt%, or even from about 0.3 to about 0.70 wt%.
• Metal from the metal alkylthiophosphate such as zinc, may also be supplied at a concentration of from about 0.02 to about 0.2 wt% zinc, or from about 0.025 to 0.19 wt%, or even from about 0.03 to about 0.18 wt% zinc. Such levels may be associated with a metal alkylthiophosphate concentration of from about 0.2 to about 2 wt%, or from about 0.25 to 1.9 wt%, or even from about 0.3 to about 1.8 wt%.
• the metal alkylthiophosphate can provide from 0.01 or from 0.02 to about 0.095 wt% phosphorus, or from about 0.025 to 0.085 wt%, or even from about 0.03 to about 0.075 wt% phosphorus.
• the metal alkylthiophosphate can provide from 0.01 or from 0.02 to about 0.2 wt% phosphorus, or from about 0.025 to 0.19 wt%, or even from about 0.03 to about 0.18 wt% phosphorus.
• the lubricant composition can also contain other sulfur containing compounds, such as, for example, organo-sulfides, including polysulfides, such as sulfurized olefins, thiadiazoles and thiadiazole adducts such as post treated dispersants.
• organo-sulfides including polysulfides, such as sulfurized olefins, thiadiazoles and thiadiazole adducts such as post treated dispersants.
• the organo-sulfide can be present in a range of 0 wt % to 6 wt %, 4 wt % to 6 wt %, 0.5 wt % to 3 wt %, 3 wt % to 5 wt %, 0 wt % to 1 wt %, 0.1 wt % to 0.5 wt %, 1% to 3%, 2% to 3%, 3% to 4%, or 2% to 4% of the lubricating composition.
• the organosulfide may alternatively be a polysulfide. In one embodiment at least about 50 wt % of the polysulfide molecules are a mixture of tri- or tetra-sulfides. In other embodiments at least about 55 wt %, or at least about 60 wt % of the polysulfide molecules are a mixture of tri- or tetra-sulfides.
• the polysulfides include sulfurized organic polysulfides from oils, fatty acids or ester, olefins or polyolefins.
• Oils which may be sulfurized include natural or synthetic oils such as mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and synthetic unsaturated esters or glycerides.
• natural or synthetic oils such as mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and synthetic unsaturated esters or glycerides.
• Fatty acids include those that contain 8 to 30, or 12 to 24 carbon atoms.
• Examples of fatty acids include oleic, linoleic, linolenic, and tall oil.
• Sulfurized fatty acid esters prepared from mixed unsaturated fatty acid esters such as are obtained from animal fats and vegetable oils, including tall oil, linseed oil, soybean oil, rapeseed oil, and fish oil.
• the polysulfide may also be derived from an olefin derived from a wide range of alkenes, typically having one or more double bonds.
• the olefins in one embodiment contain 3 to 30 carbon atoms. In other embodiments, olefins contain 3 to 16, or 3 to 9 carbon atoms.
• the sulfurized olefin includes an olefin derived from propylene, isobutylene, pentene, or mixtures thereof.
• the polysulfide comprises a polyolefin derived from polymerizing, by known techniques, an olefin as described above.
• the polysulfide includes dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized dicyclopentadiene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons.
• Examples of a thiadiazole include 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole, a hydro-carbylthio-substituted 2,5-dimercapto-1,3-4-thiadiazole, or oligomers thereof.
• the oligomers of hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole typically form by forming a sulfur-sulfur bond between 2,5-dimercapto-1,3-4-thiadiazole units to form oligomers of two or more of said thiadiazole units. Further examples of thiadiazole compounds are found in WO 2008,094759 , paragraphs 0088 through 0090.
• the disclosed technology in general provides a method of more substantially reducing friction/traction and the roughness of a metal surface.
• the method includes placing the metal surface under boundary or mixed lubrication conditions in the presence of the lubricant, that is, providing to the metal surface the lubricant composition as described herein.
• boundary or mixed conditions means operating conditions under which the metal surface of a device is in such proximity to another surface that some physical contact between asperities on the metal surface and asperities on the other surface is possible during operation of the device.
• boundary or mixed lubrication conditions it is meant that the metal surface of a device is subject to boundary or mixed conditions with another surface and the device is operated such that the boundary conditions exist.
• An example of placing a metal surface under boundary conditions includes the operation of a gear on a driveline device, in which the gears are in such close proximity that some physical contact of the gear surfaces is possible.
• the technology also provides a method of improving the operating temperatures of a gear at high load and low speed conditions, by lubricating the gears with the lubricant composition and operating the gear.
• the technology also provides a method of improving the operating efficiency of a gear, by lubricating the gear with the lubricant composition and operating the gear.
• the technology provides a method of improving the operating efficiency of a used gear, by lubricating the gear with the lubricant composition and operating the gear.
• used gear it means a gear that has been in operation in it intended application.
• an automotive gear employed in the operation of an automotive vehicle would be considered a used gear, or an industrial gear employed in its industrial application would be considered a used gear.
• the disclosed technology provides a method of lubricating a driveline device, comprising supplying thereto a lubricant composition as described herein, that is, a lubricant composition containing (a) an oil of lubricating viscosity and (c) a metal alkylthiophosphate, or in some instance, (a) an oil of lubricating viscosity, (b) an amine alkyl(thio)phosphate, and (c) a metal alkylthiophosphate, and operating the driveline device for a sufficient period to allow the lubricant composition to reduce the friction/traction and roughness of metal surfaces on the driveline device in a controlled manner to a greater extent than a typical gear lubricant.
• This reduction in surface roughness can be visually observed, or deduced in other ways, such as by a measured reduction in traction coefficient between two metal surfaces in the device, or by efficiency measurements on the driveline device before and after operation with the lubricant composition.
• the driveline device may comprise a gear as in a gearbox of a vehicle (e.g., a manual transmission) or in an axle or differential, or in other driveline power transmitting driveline devices.
• the driveline device may also include bearings.
• Lubricated gears may include hypoid gears, such as those for example in a rear drive axle.
• the lubricant should be able to meet the other aspects expected of it in normal operation of the driveline device.
• condensation product is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product.
• an acid e.g., an acid halide, anhydride, or ester
• a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction.
• the resulting product is still considered a condensation product.
• each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
• each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
• hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
• hydrocarbyl groups include:
• Samples 1 and 2 were prepared according to the recipe in Table 1. Testing was completed under ambient conditions with a changing speed profile to allow gradual reduction in the lubricant film from hydrodynamic to boundary. A single stress (160ksi) was maintained over the range of speeds. Traction coefficients were measured for each fluid in duplicate over seven stages. Table 1. - Sample formulations 1-2.
• Sample 1 Sample 2 Synthetic basestock 75.4 75.4 Olefin copolymer 14.6 14.6 Succinimide dispersant 1.32 1.32 Substituted thiadiazole 0.6 0.6 Phosphoric acid ester/amine salt 1.2 1.2 Dialkyl hydrogen phosphate 0.2 0.2 Substituted triazole 0.05 0.05 Sulfurized olefin A 4.5 Sulfurized olefin B 4.5 Secondary ZDDP 0.31 Glycerol ester 0.2 KV at 40°C 65.48 60.89 KV at 100°C 11.53 10.95 VI 172 174 P, ppm 1210 1474 S, ppm 21080 24830 Zn, ppm 377 Test conditions were:
• stage 1 The reduction in entraining velocity from stage 1 to stage 6 takes the lubrication regime from hydrodynamic to boundary. As the entraining velocity decreases, the oil film thickness decreases, the asperity interaction increases, and the traction coefficient increases to a maximum in stage 6. In stage 7, the entrainment velocity increases to be identical to stage 4. The relative difference in traction between these conditions is one indicator that surface modification and roughness reduction has been achieved during stages 5 and 6 which are intended to operate in mixed and boundary contact. A reduction in traction coefficient from stage 4 to 7 is expected if roughness has been reduced. Table 2.
• Stage 1 Stage 2 Stage 3 Stage 4 Stage 5 Stage 6 Stage 7
• Commercial 0.029 0.04 0.057 0.097 0.107 0.109 0.094
• Sample 1 0.057 0.075 0.09 0.101 0.106 0.109 0.1
• Sample 2 0.043 0.051 0.064 0.09 0.112 0.127 0.083
• Sample 3 Sample 4 Sample 5
• Glycerol ester 2 Low molecular weight secondary ZDDP 0.6 KV at 40°C 28.66 28.83 29.54 28.63 KV at 100°C 5.899 5.916 5.969 5.887 VI 156 156 153 156 P, ppm 1173 1223 1228 1256 S, ppm 19768 20935 20446 21046 Zn, ppm 707
• Samples 3-6 were evaluated on the WAM ball-on-disc test machine under identical conditions to those outlined for samples 1 and 2. While samples 1 and 2 were evaluated after only one cycle, samples 3 - 6 were evaluated by repeating the seven-stage procedure six times. Traction measurements were made at each stage and roughness measurements were made both within the contact zone and outside of the contact zone after all six cycles were completed. Traction measurements are recorded in the table below over all seven stages for both the first and the last cycle. Table 5. Traction coefficients for samples 3-6.
• Samples 7-10 Additional traction data was gathered for Samples 7-10.
• Samples 7 and 8 are identical, except that sample 8 contains both a S-containing phos ester amine salt and ZDDP.
• Samples 9 and 10 are identical to each other, but Sample 10 contains both a S-free phos ester amine salt and ZDDP.
• MTM mini-traction machine
• SRR slide-to-roll ratio
• Sample 7 Sample 8
• Sample 9 Sample 10 250 0.1506 0.1563 0.1397 0.1449 500 0.1481 0.1581 0.1415 0.1467 1000 0.1499 0.1581 0.1417 0.1495 2000 0.1509 0.1523 0.1399 0.1445 12250 0.1465 0.0595 0.1373 0.1062 12500 0.1473 0.0582 0.138 0.106 13000 0.1485 0.0576 0.1379 0.104 14000 0.1506 0.0552 0.1373 0.1029
• axle efficiency for Sample 2 was measured on a used axle (medium duty axle with 25000 miles service).
• Testing included running steady state conditions before and after a conditioning period consisting of extended speed-load cycling. Steady state conditions consisted of one temperature (80C) at high and low pinion speeds and five loads (pinion torque).
• the gear conditioning period was divided into two stages. The first stage was conducted at 79°C, while the second stage was conducted at 93°C. Each stage was run at 11 different pinion speeds (approximately 250-3000 RPM) and seven different pinion torques (approximately 50-200 lb-ft).
• gear oil fluids containing ZDDP can also improve operating temperatures at high load, low speed conditions.
• a modified L-37 test was developed with controlled air flow instead of cooling water during the test phase. This allowed the test temperature to fluctuate as it would in operation rather than operate in a controlled manner as is typical of industry testing.
• the test phase is modified from standard practice in D6121.
• the axle sump temperature direct control is removed, allowing the axle to float to any temperature below the operator safety shutoff of 190 °C.
• the axle is kept from reaching excessive temperatures by a constant velocity and trajectory of controlled air pushed over the axle and through the enclosure at 7.11 meters/second through an entry duct above the center housing with diameter of 15.24 centimeters.
• load is set to 13% contact stress reduction load setpoints specified in D6121-16a section A9.4 (1645Nm +- 34Nm) using a non-load-reduced axle batch to help further decrease risk of exceeding temperature limits without cooling water control.
• Table 12 shows the results of these evaluations and confirms that use of ZDDP in a gear oil fluid results in a substantial decrease in operating temperature in the modified L-37 test. Both fluids show exceptional wear performance. Table 12. Operating temperatures in modified L-37 testing for samples 11 - 12. Peak Temp Final Temp Pinion/ring wear Sample 11 164.9 115 8/9 Sample 12 144.4 110 9/9
• the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
• the term also encompass, as alternative embodiments, the phrases “consisting essentially of” and “consisting of,” where “consisting of' excludes any element or step not specified and “consisting essentially of” permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.
• the expression “consisting of” or “consisting essentially of,” when applied to an element of a paragraph, is intended to restrict all species of the type represented by that element, notwithstanding the presence of "comprising” elsewhere in the paragraph.

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