WO2009145824A2 - Composition de lubrifiant avec une résistance au dépôt de vernis améliorée - Google Patents

Composition de lubrifiant avec une résistance au dépôt de vernis améliorée Download PDF

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Publication number
WO2009145824A2
WO2009145824A2 PCT/US2009/001983 US2009001983W WO2009145824A2 WO 2009145824 A2 WO2009145824 A2 WO 2009145824A2 US 2009001983 W US2009001983 W US 2009001983W WO 2009145824 A2 WO2009145824 A2 WO 2009145824A2
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Prior art keywords
lubricating oil
less
group
acid
demulsifier
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PCT/US2009/001983
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English (en)
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WO2009145824A3 (fr
Inventor
Andrea Blandford Wardlow
David G. L. Holt
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Exxonmobil Research And Engineering Company
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Priority to JP2011501849A priority Critical patent/JP2011516637A/ja
Priority to EP09755187A priority patent/EP2288681A2/fr
Priority to CN200980112137.3A priority patent/CN101983230B/zh
Publication of WO2009145824A2 publication Critical patent/WO2009145824A2/fr
Publication of WO2009145824A3 publication Critical patent/WO2009145824A3/fr

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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
    • 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
    • C10M2203/04—Well-defined cycloaliphatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2040/135—Steam engines or turbines
    • 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
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • Lubricants are typically marketed based upon features such as fluid durability, deposit control, antiwear protection, filterability, water tolerance, rust/corrosion protection, and viscosity.
  • Deposit varnish is measured using a 504 hour 120 0 C DRY-TOST sludge test, which is a modified waterless ASTM D943 TOST test.
  • This DRY- TOST test method was developed by Mitsubishi Heavy Industries in order to evaluate in short time the sludge or varnish formation tendency of turbine oils.
  • the Dry-TOST conforms to the ASTM D943 test with the modified conditions shown in the table below.
  • the sludge or varnish amount equals to the amount of filter residues that lOOg of oil is filtered through a l ⁇ m Millipore filter.
  • a sludge amount of less than lOOmg/kg (ppm) is an acceptable result.
  • the table below lists the items and test conditions for this test.
  • API Group II and III base stock oils and GTL are typically better than API Group I base oils.
  • Group II and II base stocks are better because of the oxidation stability of hydroproceesed or hydrocracked base stocks as well as enhanced viscosity and temperature properties compared to conventional solvent refined base stocks. Consequently, many lubricants are being formulated with API Group II and III base stock.
  • a known deficiency of these non-polar, high saturated API Group II and III base stocks are their lower ability to solubilize or suspend lubricant degradation by-products in solution once formed. For this reason , API Group II/III based lubricants are more susceptible to deposit formation once oil degradation has began.
  • a lubricating oil with favorable deposit control comprises, a major amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof, a mannich based dispersant comprising at least 0.1 and less than 2.0 weight percent of the lubricating oil, a demulsifier comprising a polyol ester and a poly oxyakylene, the demulsifiers comprising at least 0.002 to less than 2.0 weight percent of the lubricating oil, the lubricating oil has a deposit control value less than 60 using 504 hour 120°C DRY TOST sludge test.
  • a method to improve deposit control is disclosed.
  • This method comprises, obtaining a lubricating oil comprising a major amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof, a mannich based dispersant comprising at least 0.1 and less than 2.0 weight percent of the lubricating oil, a demulsif ⁇ er comprising a polyol ester and a poly oxyakylene, the demulsifiers comprising at least 0.002 to less than 2.0 weight percent of the lubricating oil, wherein the lubricating oil has a deposit control value less than 60 using 504 hour 12O 0 C DRY TOST sludge test and lubricating with the lubricating oil.
  • a method of formulating a lubricating oil to improve deposit control and emulsion properties comprises obtaining a major amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof, a mannich based dispersant comprising at least 0.1 and less than 2.0 weight percent of the lubricating oil, a demulsif ⁇ er comprising a polyol ester and a poly oxyakylene, the demulsifiers comprising at least 0.002 to less than 2.0 weight percent of the lubricating oil, and blending the base stocks, demulsifiers and dispersants to have a deposit control value less than 60 using 504 hour 12O 0 C DRY TOST sludge test.
  • a lubricant composition that comprises either a API Group II or III or GTL base stocks or combinations thereof with antioxidants and other additive when formulated with a specific mannich-based dispersant/demulsif ⁇ er combination yields an unexpected improvement in deposit control while maintaining good demulsability.
  • a specific mannich-based dispersant/demulsif ⁇ er combination yields an unexpected improvement in deposit control while maintaining good demulsability.
  • dispersants are known to improve deposit control, they are polar in nature and tend to be emulsive and provide poor water separation.
  • An additional benefit in one embodiment of this lubricant composition is that the final product also exhibit good demulsification by ASTM D- 1401. This method is a rapid test that involves mixing together 40ml of oil and 40 ml of water for 5 minutes at 1500 rpm with an impeller. The mixture is allowed to stand and the time for the water, oil and any emulsion phase to separate is recorded. This test is conducted at 54°C (130 0 F) for viscosity below 90 cSt at 40 0 C. a generally acceptable result is 30 minutes maximum time to 3 mis of emulsion remaining.
  • the acceptable treat ranges for the mannich based dispersants is at least 0.1 to less than 2.0 weight percent.
  • a preferred treat range is at least 0.2 to less than 0.5 weight percent and a most preferred treat range is 0.2 and less than 0.4 weight percent.
  • a Pluronic L 121 Surfactant from BASF is effective at the same concentration as the polyol ester.
  • the demulsifier also includes a propylene oxide block copolymer.
  • the preferred concentration of the polyol ester and ethylene oxide in the demulsifier is at least .001 and not more than .1 wt%. Most preferably, the concentration should be at least .6 wt% and less than .05 wt%. In this embodiment, higher ethylene oxide contents or higher MW tend to be less effective for demulsiblity.
  • the ethylene oxide content in Pluronic L 121 is 10 wt% and average molecular weight is 4400. In a preferred embodiment, a 25 wt% ethylene oxide or polyol ester and a molecular weight of 5000 would be the upper limit of acceptability of an ethylene oxide or polyol ester in the demulsifier additive.
  • the acceptable treat ranges for the demulsifiers is at least 0.002 to less than 2.0 weight percent.
  • a preferred treat range is at least 0.01 to less than 0.1 weight percent and a most preferred treat range is 0.01 and less than 0.05 weight percent.
  • the formulation demonstrates excellent varnish deposit properties using the 504 hour 120C DRY TOST sludge test.
  • the formulation should be a value less than 60, more preferably a value less than 50 and most preferably a value less than 25.
  • the claimed invention provides excellent electrical conductivity ("EC").
  • the test used was D-4308 at 32 °F.
  • a sample of liquid hydrocarbon is introduced into a clean conductivity cell which is connected in series to a battery voltage source and a sensitive dc ammeter.
  • the conductivity automatically calculated from the observed peak current reading dc voltage and cell constant using Ohm's law, appears as a digital value in either a manual or automatic mode of meter operation.
  • Low electrical conductivity can results in static charge build up when machines are shutdown or idling. Having higher electrical conductivity can prevent a phenomena of static discharge which has been implicated as one root cause of varnish deposit formation in gas turbines equipped with fine filtration and operating at high flowrate.
  • the electrical conductivity should be at least 50 pS/m and more preferably at least 60 pS/m and most preferably greater than 100 pS/m.
  • the formulation should have low amounts of calcium and zinc.
  • the preferred embodiment is less than 5 PPM zinc and less than 5 PPM calcium.
  • the more preferred embodiment is less than 5 PPM zinc and less than 5 PPM calcium and less than 50 PPM phosphorus
  • An even more preferred embodiment is less than 1 PPM zinc, less than 1 PPM calcium and less than 5 PPM phosphorous.
  • the formulation would comprise at least one additive selected form the group consisting of an antiwear additive, metal passivator, demulsifier, pour point depressant, rust inhibitor, defoamant and any combination thereof. Additional information regarding base stocks and additives are provided below.
  • calcium containing additive such as calcium sulfonates, would not be used due potential reaction to form calicuim carboxylate soaps with commonly used ashless rust inhibitors used in typical formulations.
  • Groups I, II, III, IV and V are broad categories of base oil stocks 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 generally 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 generally 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 stock generally has a viscosity index greater than about 120 and contains less than or equal to about 0.03 % sulfur and greater than about 90% saturates.
  • Group IV includes polyalphaolefins (PAO).
  • Group V base stocks include base stocks not included in Groups I-IV. Table 1 summarizes properties of each of these five groups.
  • Group I ⁇ 90% and/or > 0.03% and > 80 and ⁇ 120
  • Group II > 90% and ⁇ 0.03% and > 80 and ⁇ 120
  • PAO Polyalphaolefins
  • the base stocks include at least one base stock of synthetic oils and most preferably include at least one base stock of API group IV Poly Alpha Olefins.
  • Synthetic oil for purposes of this application shall include all oils that are not naturally occurring mineral oils. Naturally occurring mineral oils are often referred to as API Group I oils.
  • Gas to liquid (GTL) base stocks can also be preferentially used with the components of this invention as a portion or all of the base stocks used to formulate the finished lubricant.
  • GTL Gas to liquid
  • 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 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 feedstocks.
  • GTL base stock(s) include oils boiling in the lube oil boiling range separated/fractionated from GTL materials such as by, for example, distillation or thermal diffusion, and subsequently subjected to well-known catalytic or solvent dewaxing processes to produce lube oils of reduced/low pour point; wax isomerates, comprising, for example, hydroisomerized or isodewaxed synthesized hydrocarbons; hydro- isomerized or isodewaxed Fischer-Tropsch ("F-T") material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydroisomerized or isodewaxed F-T hydrocarbons or hydroisomerized or isodewaxed F-T waxes, hydroisomerized or isodewaxed synthesized waxes, or mixtures thereof.
  • F-T Fischer-Tropsch
  • GTL base stock(s) derived from GTL materials especially, hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax derived base stock(s) are characterized typically as having kinematic viscosities at 100 0 C of from about 2 mm /s to about 50 mm 2 /s, preferably from about 3 mm 2 /s to about 50 mm 2 /s, more preferably from about 3.5 mm 2 /s to about 30 mm 2 /s, as exemplified by a GTL base stock derived by the isodewaxing of F-T wax, which has a kinematic viscosity of about 4 mm 2 /s at 100 0 C and a viscosity index of about 130 or greater.
  • GTL base oil/base stock and/or wax isomerate base oil/base stock as used herein and in the claims is to be understood as embracing individual fractions of GTL base stock/base oil or wax isomerate base stock/base oil as recovered in the production process, mixtures of two or more GTL base stocks/base oil fractions and/or wax isomerate base stocks/base oil fractions, as well as mixtures of one or two or more low viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) with one, two or more high viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) to produce a bi-modal blend wherein the blend exhibits a viscosity within the aforesaid recited range.
  • Kinematic Viscosity refers to a measurement made by ASTM method D445.
  • GTL base stocks and base oils derived from GTL materials are further characterized typically as having pour points of about -5°C or lower, preferably about -10 0 C or lower, more preferably about -15°C or lower, still more preferably about -20 0 C or lower, and under some conditions may have advantageous pour points of about -25 0 C or lower, with useful pour points of about -30 0 C to about -40 0 C or lower. If necessary, a separate dewaxing step may be practiced to achieve the desired pour point.
  • pour point refer to measurement made by ASTM D97 and similar automated versions.
  • the GTL base stock(s) derived from GTL materials, especially hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax-derived base stock(s) which are base stock components which can be used in this invention are also characterized typically as having viscosity indices of 80 or greater, preferably 100 or greater, and more preferably 120 or greater. Additionally, in certain particular instances, viscosity index of these base stocks may be preferably 130 or greater, more preferably 135 or greater, and even more preferably 140 or greater.
  • GTL base stock(s) that derive from GTL materials preferably F-T materials especially F-T wax generally have a viscosity index of 130 or greater. References herein to viscosity index refer to ASTM method D2270.
  • the GTL base stock(s) are typically highly paraffinic of greater than 90 percent saturates) and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used.
  • GTL base stocks and base oils 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 and base oil obtained by the hydroisomerization/isodewaxing of F-T material, especially F-T wax is essentially nil.
  • the GTL base stock(s) comprises paraffinic materials that consist predominantly of non-cyclic isoparaffins and only minor amounts of cycloparaffins.
  • These GTL base stock(s) typically comprise paraffinic materials that consist of greater than 60 wt% non-cyclic isoparaffins, preferably greater than 80 wt% non-cyclic isoparaffins, more preferably greater than 85 wt% non-cyclic isoparaffins, and most preferably greater than 90 wt% non-cyclic isoparaffins.
  • compositions of GTL base stock(s), hydroisomerized or isodewaxed F-T material derived base stock(s), and wax-derived hydroisomerized/isodewaxed base stock(s), such as wax isomerates/isodewaxates are recited in U.S. Pat. Nos. 6,080,301; 6,090,989, and 6, 165,949 for example.
  • the additives may be chosen to modify various properties of the lubricating oils.
  • the additives should provide the following properties, antiwear protection, rust protection, micropitting protection, friction reduction, and improved filterability.
  • Persons skilled in the art will recognize various additives that can be chosen to achieve favorable properties including favorable properties for gear oil applications.
  • additives well known as functional fluid additives in the art can also be incorporated in the functional fluid composition of the invention, in relatively small amounts, if desired; frequently, less than about 0.001% up to about 10-20% or more.
  • at least one oil additive is added from the group consisting of antioxidants, stabilizers, antiwear additives, dispersants, detergents, antifoam additives, viscosity index improvers, copper passivators, metal deactivators, rust inhibitors, corrosion inhibitors, pour point depressants, demulsifiers, anti-wear agents, extreme pressure additives and friction modifiers.
  • the additives listed below are non-limiting examples and are not intented to limit the claims.
  • Dispersants should contain the alkenyl or alkyl group R has an Mn value of about 500 to about 5000 and an Mw/Mn ratio of about 1 to about 5. The preferred Mn intervals depend on the chemical nature of the agent improving filterability.
  • Polyolefinic polymers suitable for the reaction with maleic anhydride or other acid materials or acid forming materials include polymers containing a predominant quantity of C2 to C5 monoolefins, for example, ethylene, propylene, butylene, isobutylene and pentene.
  • a highly suitable polyolefinic polymer is polyisobutene.
  • the succinic anhydride preferred as a reaction substance is PIBSA, that is, polyisobutenyl succinic anhydride.
  • the dispersant contains a succinimide comprising the reaction product of a succinic anhydride with a polyamine
  • the alkenyl or alkyl substituent of the succinic anhydride serving as the reaction substance consists preferably of polymerised isobutene having an Mn value of about 1200 to about 2500. More advantageously, the alkenyl or alkyl substituent of the succinic anhydride serving as the reaction substance consists in a polymerised isobutene having an Mn value of about 2100 to about 2400.
  • the agent improving filterability contains an ester of succinic acid comprising the reaction product of a succinic anhydride and an aliphatic polyhydric alcohol
  • the alkenyl or alkyl substituent of the succinic anhydride serving as the reaction substance consists advantageously of a polymerised isobutene having an Mn value of 500 to 1500.
  • a polymerised isobutene having an Mn value of 850 to 1200 is used.
  • Amides suitable uses of amines include antiwear agents, extreme pressure additives, friction modifiers or Dispersants.
  • the amides which are utilized in the compositions of the present invention may be amides of mono- or polycarboxylic acids or reactive derivatives thereof.
  • the amides may be characterized by a hydrocarbyl group containing from about 6 to about 90 carbon atoms; each is independently hydrogen or a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or a heterocyclic-substituted hydrocarbyl group, provided that both are not hydrogen; each is, independently, a hydrocarbylene group containing up to about 10 carbon atoms; AIk is an alkylene group containing up to about 10 carbon atoms.
  • the amide can be derived from a monocarboxylic acid, a hydrocarbyl group containing from 6 to about 30 or 38 carbon atoms and more often will be a hydrocarbyl group derived from a fatty acid containing from 12 to about 24 carbon atoms.
  • the amide is derived from a di- or tricarboxylic acid, will contain from 6 to about 90 or more carbon atoms depending on the type of polycarboxylic acid. For example, when the amide is derived from a dimer acid, will contain from about 18 to about 44 carbon atoms or more, and amides derived from trimer acids generally will contain an average of from about 44 to about 90 carbon atoms.
  • Each is independently hydrogen or a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or a heterocyclic-substituted hydrocarbon group containing up to about 10 carbon atoms.
  • heterocyclic substituted hydrocarbyl groups wherein the heterocyclic substituent is derived from pyrrole, pyrroline, pyrrolidine, morpholine, piperazine, piperidine, pyridine, pipecoline, etc.
  • Specific examples include methyl, ethyl, n-propyl, n-butyl, n-hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, amino-methyl, aminoethyl, aminopropyl, 2-ethylpyridine, 1- ethylpyrrolidine, 1-ethylpiperidine, etc.
  • the alkyl group can be an alkylene group containing from 1 to about 10 carbon atoms.
  • alkylene groups include, methylene, ethylene, propylene, etc.
  • hydrocarbylene groups and in particular, alkylene group containing up to about 10 carbon atoms.
  • hydrocarbylene groups include, methylene, ethylene, propylene, etc.
  • the amide contains at least one morpholinyl group. In one embodiment, the morpholine structure is formed as a result of the condensation of two hydroxy groups which are attached to the hydrocarbylene groups.
  • the amides are prepared by reacting a carboxylic acid or reactive derivative thereof with an amine which contains at least one >NH group.
  • Aliphatic monoamines include mono-aliphatic and di-aliphatic- substituted amines wherein the aliphatic groups may be saturated or unsaturated and straight chain or branched chain.
  • Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and dialkenyl-substituted amines, etc.
  • Specific examples of such monoamines include ethyl amine, diethyl amine, n- butyl amine, di-n-butyl amine, isobutyl amine, coco amine, stearyl amine, oleyl amine, etc.
  • a cycloaliphatic-substituted aliphatic amine is 2- (cyclohexyl)-ethyl amine.
  • heterocyclic-substituted aliphatic amines include 2-(2-aminoethyl)-pyrrole, 2-(2-aminoethyl)-l -methyl pyrrole, 2-(2- aminoethyl)-l-methylpyrrolidine and 4-(2-aminoethyl)morpholine, l-(2- aminoethyl)piperazine, l-(2-aminoethyl)piperidine, 2-(2-aminoethyl)pyridine, 1- (2-aminoethyl)pyrrolidine, l-(3-aminopropyl)imidazole, 3-(2- aminopropyl)indole, 4-(3-aminopropyl)mo ⁇ holine, 1 -(3-aminopropyl)-2- pipeco
  • Cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure.
  • Examples of cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine, dicyclohexylamines, and the like.
  • Aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
  • the aromatic ring will usually be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
  • aromatic monoamines examples include aniline, di-(para- methylphenyl)amine, naphthylamine, N-(n-butyl)-aniline, and the like.
  • aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-ethoxy-aniline, para-dodecylaniline, cyclohexyl- substituted naphthylamine, phenathiazines, and thienyl-substituted aniline.
  • Polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to the above-described monoamines except for the presence within their structure of additional amino nitrogens.
  • the additional amino nitrogens can be primary, secondary or tertiary amino nitrogens.
  • Examples of such polyamines include N-amino-propyl-cyclohexylamines, N,N'-di-n-butyl-paraphenylene diamine, bis-(para-aminophenyl)methane, 1,4-diaminocyclohexane, and the like.
  • the hydroxy-substituted amines contemplated are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, they have hydroxy groups capable of functioning as alcohols.
  • examples of such hydroxy-substituted amines include ethanolamine, di-(3-hydroxypropyl)- amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanolamine, di-(2- hydroxyamine, N-(hydroxypropyl)-propylamine, N-(2-methyl)- cyclohexylamine, 3 -hydroxy cyclopentyl parahydroxyaniline, N-hydroxyethal piperazine and the like.
  • the amines useful in the present invention are alkylene polyamines including hydrogen, or a hydrocarbyl, amino hydrocarbyl, hydroxyhydrocarbyl or heterocyclic-substituted hydrocarbyl group containing up to about 10 carbon atoms
  • AIk is an alkylene group containing up to about 10 carbon atoms, and is 2 to about 10.
  • AIk is ethylene or propylene.
  • a will have an average value of from 2 to about 7.
  • alkylene polyamines examples include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc.
  • Alkylene polyamines include ethylene diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, and the like. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines are useful, as are mixtures of two or more of any of the afore-described polyamines.
  • Ethylene polyamines such as those mentioned above, are especially useful for reasons of cost and effectiveness.
  • Such polyamines are described in detail under the heading "Diamines and Higher Amines” in The Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages 27- 39, Interscience Publishers, Division of John Wiley and Sons, 1965, which is hereby incorporated by reference for the disclosure of useful polyamines.
  • Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.
  • polyamine bottoms can be characterized as having less than 2, usually less than 1% (by weight) material boiling below about 200. degree. C.
  • ethylene polyamine bottoms which are readily available and found to be quite useful, the bottoms contain less than about 2% (by weight) total diethylene triamine (DETA) or triethylene tetramine (TETA).
  • DETA diethylene triamine
  • TETA triethylene tetramine
  • the dispersants are selected from: Mannich bases that are condensation reaction products of a high molecular weight phenol, an alkylene polyamine and an aldehyde such as formaldehyde, Succinic-based dispersants that are reaction products of a olefin polymer and succinic acylating agent (acid, anhydride, ester or halide) further reacted with an organic hydroxy compound and/or an amine.
  • Mannich bases that are condensation reaction products of a high molecular weight phenol, an alkylene polyamine and an aldehyde such as formaldehyde
  • Succinic-based dispersants that are reaction products of a olefin polymer and succinic acylating agent (acid, anhydride, ester or halide) further reacted with an organic hydroxy compound and/or an amine.
  • High molecular weight amides and esters such as reaction products of a hydrocarbyl acylating agent and a a polyhydric aliphatic alcohol (such as glycerol, pentaerythritol or sorbitol).
  • a hydrocarbyl acylating agent such as glycerol, pentaerythritol or sorbitol.
  • Ashless (metal-free) polymeric materials that usually contain an oil soluble high molecular weight backbone linked to a polar functional group that associates with particles to be dispersed are typically used as dispersants.
  • hydrocarbon backbone materials are olefin polymers and copolymers, i.e.—ethylene, propylene, butylene, isobutylene, styrene; there may or may not be further functional groups incorporated into the backbone of the polymer, whose molecular weight ranges from 300 up to 5000.
  • Polar materials such as amines, alcohols, amides or esters are attached to the backbone via a bridge.
  • Antioxidants include sterically hindered alkyl phenols such as 2,6-di- tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-(2-octyl-3- propanoic) phenol; N,N-di(alkylphenyl) amines; and alkylated phenylene- diamines.
  • the antioxidant component may be a hindered phenolic antioxidant such as butylated hydroxytoluene, suitably present in an amount of 0.01 to 5%, preferably 0.4 to 0.8%, by weight of the lubricant composition.
  • component b) may comprise an aromatic amine antioxidant such as mono-octylphenylalphanapthylamine or p,p-dioctyldiphenylamine, used singly or in admixture.
  • the amine anti-oxidant component is suitably present in a range of from 0.01 to 5% by weight of the lubricant composition, more preferably 0.5 to 1.5%.
  • the amine-type antioxidant includes, for example, monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamines such as 4,4'- dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine and 4,4'- dinonyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine and tetranonyldiphenylamine; and naphthylamines such as .
  • monoalkyldiphenylamines such as monooctyldiphenylamine and mono
  • Oxidation inhibitors organic compounds containing nitrogen, phosphorus and some alkylphenols are also employed.
  • 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; with ratios of amine / phenolic to be from 1 : 10 to 10: 1 of the mixtures prefered.
  • phenol-based antioxidants examples 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.
  • Yonox SS n-dodecyl-3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate and 2'-ethylhexyl-3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate; 2,6-di-t-butyl-.alpha.-dimethylamino-p-cresol, 2,2'- methylenebis(4-alkyl ⁇ 6-t-butylphenol) compounds such as 2,2'-methylenebis(4- methyl-6-t-butylphe- nol) (manufactured by the Kawaguchi Kagaku Co.
  • Antage W-400 2,2'-methylenebis(4-ethyl-6-t- butylphenol)
  • Kawaguchi Kagaku Co. 2,2'-methylenebis(4-ethyl-6-t- butylphenol)
  • Antage W-500 bisphenols such as 4,4'-butylidenebis(3-methyl-6- t-butyl- phenol) (manufactured by the Kawaguchi Kagaku Co.
  • Yoshinox 930 l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4 ⁇ hydroxybenzyl)benzene (manufactured by Ciba Speciality Chemicals under the trade designation "Irganox 330”), bis[3,3'-bis(4'-hydroxy-3'-t-butylpheny- l)butyric acid] glycol ester, 2-(3',5'-di-t-butyl-4-hydroxyphenyl)-methyl ⁇ 4- (2",4"-di-t-butyl-3"-hydroxyphenyl)methyl-6-t-butylphenol and 2,6-bis(2'- hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol; and phenol/aldehyde condensates such as the condensates of p-t-butylphenol and formaldehyde and the condensates of p-t-butylphenol
  • Viscosity index improvers and/or the pour point depressant include polymeric alkylmethacrylates and olefinic copolymers such as an ethylene- propylene copolymer or a styrene-butadiene copolymer or polyalkene such as PIB.
  • Viscosity index improvers VI improvers
  • high molecular weight polymers that increase the relative viscosity of an oil at high temperatures more than they do at low temperatures.
  • the most common VI improvers are methacrylate polymers and copolymers, acrylate polymers, olefin polymers and copolymers, and styrene-butadiene copolymers.
  • viscosity index improver examples include polymethacrylate, polyisobutylene, alpha-olefin polymers, alpha-olefin copolymers (e.g., an ethylene-propylene copolymer), polyalkylstyrene, phenol condensates, naphthalene condensates, a styrenebutadiene copolymer and the like.
  • polymethacrylate having a number average molecular weight of 10,000 to 300,000 and alpha-olefin polymers or alpha-olefin copolymers having a number average molecular weight of 1,000 to 30,000, particularly ethylene- alpha-olefm copolymers having a number average molecular weight of 1 ,000 to 10,000 are preferred.
  • the viscosity index increasing agents which can be used include, for example, polymethacrylates and ethylene/propylene copolymers, other non- dispersion type viscosity index increasing agents such as olefin copolymers like styrene/diene copolymers, and dispersible type viscosity index increasing agents where a nitrogen containing monomer has been copolymerized in such materials. These materials can be added and used individually or in the form of mixtures, conveniently in an amount within the range of from 0.05 to 20 parts by weight per 100 parts by weight of base oil.
  • Pour point depressors include polymethacrylates. Commonly used additives such as alkylaromatic polymers and polymethacrylates are useful for this purpose; typically the treat rates range from 0.001% to 1.0%.
  • Anti-rust additives include (short-chain) alkenyl succinic acids, partial esters thereof and nitrogen-containing derivatives thereof.
  • 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.
  • Particularly preferred anti-rust agents are indicated below.
  • Examples of Polybasic Carboxylic Acids The alkenyl (ClO-ClOO) succinic acids indicated in CAS No. 27859-58-1 and ester derivatives thereof, dimer acid, N-acyl-N-alkyloxyalkyl aspartic acid esters (U.S. Pat. No.
  • alkylamines which function as antirust addives 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,
  • 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 laurylpropylenediamines such as lauryl
  • Demulsifying agents include alkoxylated phenols and phenol- formaldehyde resins and synthetic alkylaryl sulfonates such as metallic dinonylnaphthalene sulfonates.
  • a demulsifing 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 invention may also be one produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product.
  • Functional fluids according to the invention possess a pour point of less than about -20 degree C, and exhibit compatibility with a wide range of anti- wear additive and extreme pressure additives.
  • the formulations according to the invention also are devoid of fatigue failure that is normally expected by those of ordinary skill in the art when dealing with polar lubricant base stocks.
  • Polyoxyalkylene glycols useful in the present invention may be produced by a well-known process for preparing polyalkylene oxide having hydroxy 1 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 100 degrees C to 160 degrees 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 invention may also be one produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product.
  • 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 100,00OcSt.
  • 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.
  • Metal deactivating compounds / Corrosion inhibitors include alkyltriazoles and benzotriazoles.
  • dibasic acids useful as anti- corrosion agents are adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid, 1,10-decanedicarboxylic acid, and fumaric acid.
  • the anti- corrosion combination is a straight or branch-chained, saturated or unsaturated monocarboxylic acid or ester thereof.
  • the acid is a C sub 4 to C sub 22 straight chain unsaturated monocarboxylic acid.
  • the preferred concentration of this additive is from 0.001% to 0.35% by weight of the total lubricant composition.
  • 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.
  • the triazole should be used at a concentration from 0.005% to 0.25% by weight of the total composition.
  • the preferred triazole is tolylotriazole which may be included in the compositions of the invention include triazoles, thiazoles and certain diamine compounds which are useful as metal deactivators or metal passivators. Examples include triazole, benzotriazole and substituted benzotriazoles 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. Examples of suitable compounds are benzotriazole and the tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles, octylbenzotriazoles and nitrobenzotriazoles. Benzotriazole and tolyltriazole are particularly preferred.
  • a straight or branched chain saturated or unsaturated monocarboxylic acid which is optionally sulphurised in an amount which may be up to 35% by weight; or an ester of such an acid; and a triazole or alkyl derivatives thereof, or short chain alkyl of up to 5 carbon atoms; n is zero or an integer between 1 and 3 inclusive; and is hydrogen, morpholino, alkyl, amido, amino, hydroxy or alkyl or aryl substituted derivatives thereof; or a triazole selected from 1,2,4 triazole, 1,2,3 triazole, 5-anilo-l,2,3,4-thiatriazole, 3-amino- 1,2,4 triazole, 1-H-benzotriazole-l-yl-methylisocyanide, methylene-bis- benzotriazole and naphthotriazole.
  • Alkyl is straight or branched chain and is 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 is straight or branched chain and is for example prop-2-enyl, but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl, hexa-2,4-dienyl, dec-10-enyl or eicos-2-enyl.
  • Cylcoalkyl is for example cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl or cyclododecyl.
  • Aralkyl is for example benzyl, 2- phenylethyl, benzhydryl or naphthylmethyl.
  • Aryl is for example phenyl or naphthyl.
  • the heterocyclic group is for example a morpholine, pyrrolidine, piperidine or a perhydroazepine ring.
  • Alkylene moieties include for example methylene, ethylene, 1 :2- or 1 :3- propylene, 1 :4-butylene, l :6-hexylene, l :8-octylene, l : 10-decylene and 1 : 12- dodecylene.
  • Arylene moieties include for example phenylene and naphthylene.
  • the metal deactivating agents which can be used in the lubricating oil a composition of the present invention include 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 1-alkyltolutriazoles, for example, 1- dioctylaminomethyl-2,3-tolutriazole; benzimidazole and benzimidazole derivatives or concentrates and/or mixtures thereof.
  • benzotriazole and the 4- alkylbenzotriazoles such as 4-methylbenzotriazole and 4-ethylbenzotriazole
  • 5- alkylbenzotriazoles such as 5-methylbenzotri
  • a phosphate ester or salt may be a monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl phosphate, wherein each hydrocarbyl group is saturated.
  • each hydrocarbyl group independently contains from about 8 to about 30, or from about 12 up to about 28, or from about 14 up to about 24, or from about 14 up to about 18 carbons atoms.
  • the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups and mixtures thereof.
  • 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 C 18 -C 28 primary alcohols having mostly C20 alcohols as determined by GLC (gas-liquid- chromatography)); and Alfol22+ alcohols (C 18 -C 28 primary alcohols containing primarily C 22 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 C 22 primary alcohol, about 15% of a C 20 primary alcohol and about 8% of C 18 and C 24 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 C 8 to C 18 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 C 10 alcohol, 66.0% of C 12 alcohol, 26.0% of C 14 alcohol and 6.5% of C 16 alcohol.
  • Neodol 23 is a mixture of C 12 and C 13 alcohols
  • Neodol 25 is a mixture of C 12 to C 15 alcohols
  • Neodol 45 is a mixture of C 14 to C 15 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 C 11 -C 14, and the latter is derived from a C 15 -C 18 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. Pat. No. 4,234,435.
  • the 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 invention include methylamine, ethylamine, propylamine, butylamine, cyclopentylamine, cyclohexylamine, octylamine, dodecylamine, allylamine, cocoamine, stearylamine, and laurylamine.
  • Examples of secondary monoamines include dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclopentylamine, dicyclohexylamine, methylbutylamine, ethylhexylamine, etc.
  • An amine is a fatty (C. sub.8-30) amine which includes n-octylamine, n- decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n- octadecylamine, oleyamine, etc.
  • fatty amines include commercially available fatty amines such as "Armeen” amines (products available from Akzo Chemicals, Chicago, 111.), such 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.
  • R"(OR') x NH 2 a primary ether amine
  • 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
  • R" is a hydrocarbyl group of about 5 to about 150 carbon atoms.
  • An example of an ether amine is available under the name SURFAM.RTM. amines produced and marketed by Mars Chemical Company, Atlanta, Ga.
  • Preferred etheramines are exemplified by those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear C 16), SURFAM P17B (tridecyloxypropylamine).
  • the carbon chain lengths (i.e., C 14, etc.) of the SURFAMS described above and used hereinafter are approximate and include the oxygen ether linkage.
  • An amine is a tertiary-aliphatic primary amine.
  • the aliphatic group preferably an alkyl group, contains from about 4 to about 30, or from about 6 to about 24, or from about 8 to about 22 carbon atoms.
  • the tertiary alkyl primary amines are monoamines the alkyl group is a hydrocarbyl group containing from one to about 27 carbon atoms and R 6 is a hydrocarbyl group containing from 1 to about 12 carbon atoms.
  • Such amines are illustrated by tert-butylamine, tertrhexylamine, 1 -methyl- 1-amino-cyclohexane, tert- octylamine, tert-decylamine, tert-dodecylamine, tert-tetradecylamine, tert- hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert- octacosanylamine.
  • Mixtures of tertiary aliphatic amines may also be used in preparing the phosphate salt.
  • amine mixtures of this type are "Primene 81R” which is a mixture of C 11 -C 14 tertiary alkyl primary amines and "Primene JMT” which is a similar mixture of C 18 -C 22 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.
  • the tertiary aliphatic primary amine useful for the purposes of this invention and methods for their preparation are described in U.S. Pat.
  • An amine is a heterocyclic polyamine.
  • the heterocyclic polyamines include aziridines, azetidines, azolidines, tetra- and dihydropyridines, pyrroles, indoles, piperidines, imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkyl-piperazines, N 5 N'- diaminoalkylpiperazines, azepines, azocines, azonines, anovanes and tetra-, di- and perhydro derivatives of each of the above and mixtures of two or more of these heterocyclic amines.
  • 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.
  • Lubricating compositions also may include a fatty imidazoline or a reaction product of a fatty carboxylic acid and at least one polyamine.
  • the fatty imidazoline has fatty substituents containing from 8 to about 30, or from about 12 to about 24 carbon atoms. The substituent may be saturated or unsaturated, heptadeceneyl derived oleyl groups, preferably saturated.
  • the fatty imidazoline may be prepared by reacting a fatty carboxylic acid with a polyalkylenepolyamine, such as those discussed above.
  • 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.
  • Hydroxyalkyl groups are to be understood as meaning, for example, monoethanolamine, diethanolamine or triethanolamine, and the term amine also includes diamine.
  • the amine used for the neutralization depends on the phosphoric esters used.
  • the EP additive according to the invention has the following advantges: It very high effectiveness when used in low concentrations and it is free of chlorine. For the neutralization of the phosphoric esters, the latter are taken and the corresponding amine slowly added with stirring. The resulting heat of neutralization is removed by cooling.
  • the EP additive according to the invention can be incorporated into the respective base liquid with the aid of fatty substances (e.g. tall oil fatty acid, oleic acid, etc.) as solubilizers.
  • the base liquids used are napthenic or paraffinic base oils, synthetic oils (e.g. polyglycols, mixed polyglycols), polyolefins, carboxylic esters, etc.
  • the composition comprises at least one phosphorus containing extreme pressure additive.
  • additives are amine phosphate extreme pressure additives such as that known under the trade name IRGALUBE 349
  • amine phosphates are suitably present in an amount of from 0.01 to 2%, preferably 0.2 to 0.6% by weight of the lubricant composition.
  • At least one straight and/or branched chain saturated or unsaturated monocarboxylic acid which is optionally sulphurised in an amount which may be up to 35% by weight; and/or an ester of such an acid.
  • the neutral organic phosphate which forms a compoent of the formulation may be present in an amount of 0.01 to 4%, preferably 1.5 to 2.5% by weight of the composition.
  • the above amine phosphates and any of the aforementioned benzo- or tolyltriazoles can be mixed together to form a single componet capable of delievering antiwear performance.
  • the neutral organic phosphate is also a conventional ingredient of lubricating compositions and any such neutral organic phosphate falling within the formula as previously defined may be employed.
  • Phosphates for use in the present invention 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.
  • Examples of 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 of from 0.03 to 5% by weight, preferably from 0.1 to 4% by weight, relative to the total weight of the composition.
  • 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.
  • the aromatic carboxylic acids is salicylic acid.
  • the 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 monoethanolamine and diethanolamine.
  • preferred are a combination of isostearic acid and tetraethylenepentamine, and a combination of oleic acid and diethanolamine.
  • the reaction products of carboxylic acids and amines are added to the base oil in an amount of from 0.01 to 5% by weight, preferably from 0.03 to 3% by weight, relative to the total weight of the composition.
  • 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: Hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical);
  • the substituted hydrocarbon substituents that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent, hydroxy, alkoxy, nitro);
  • Hetero-atom containing substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
  • hydrocarbyl group in the context of the present invention, is also intended to encompass cyclic hydrocarbyl or hydrocarbylene groups, where two or more of the alkyl groups in the above structures together form a cyclic structure.
  • the hydrocarbyl or hydrocarbylene groups of the present invention generally are alkyl or cycloalkyl groups which contain at least 3 carbon atoms. Preferably or optimaly containg sulfur, nitrogen, or oxygen, they will contain 4 to 24, and alternatively 5 to 18 carbon atoms. In another embodiment they contain about 6, or exactly 6 carbon atoms.
  • the hydrocarbyl groups can be tertiary or preferably primary or secondary groups; in one embodiment the component is a di(hydrocarbyl)hydrogen phosphite and each of the hydrocarbyl groups is a primary alkyl group; in another embodiment the component is a di(hydrocarbyl)hydrogen phosphite and each of the hydrocarbyl groups is a secondary alkyl group. In yet another embodiment the component is a hydrocarbylenehydrogen phosphite.
  • Examples of straight chain hydrocarbyl groups include methyl, ethyl, n- propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, stearyl, n- hexadecyl, n-octadecyl, oleyl, and cetyl.
  • Examples of branched-chain hydrocarbon groups include isopropyl, isobutyl, secondary butyl, tertiary butyl, neopentyl, 2-ethylhexyl, and 2,6-dimethylheptyl.
  • cyclic groups include cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, and cyclooctyl.
  • aromatic hydrocarbyl groups and mixed aromatic-aliphatic hydrocarbyl groups include phenyl, methylphenyl, tolyl, and naphthyl.
  • the R groups can also comprise a mixture of hydrocarbyl groups derived from commercial alcohols. Examples of some monohydric alcohols and alcohol mixtures include the commercially available "Alfol.TM.” alcohols marketed by Continental Oil Corporation. Alfol.TM. 810, for instance, is a mixture containing alcohols consisting essentially of straight chain, primary alcohols having from 8 to 12 carbon atoms. Alfol.TM. 12 is a mixture of mostly C 12 fatty alcohols; Alfol.TM. 22+ comprises C 18-28 primary alcohols having mostly C 22 alcohols, and so on.
  • Neodol.TM Various mixtures of monohydric fatty alcohols derived from naturally occurring triglycerides and ranging in chain length from C 8 to C 18 are available from Procter & Gamble Company. "Neodol.TM.” alcohols are available from Shell Chemical Co., where, for instance, Neodol.TM. 25 is a mixture of C 12 to C 15 alcohols.
  • phosphites within the scope of the invention include phosphorous acid, mono-, di-, or tri-propyl phosphite; mono-, di-, or tri-butyl phosphite, di-, or tri-amyl phosphite; mono-, di-, or tri-hexyl phosphite; mono-, di-, or tri-phenyl; mono-, di-, or tri-tolyl phosphite; mono-, di- , or tri-cresyl phosphite; dibutyl phenyl phosphite or mono-, di-, or tri-phosphite, amyl dicresyl phosphite.
  • the phosphorus compounds of the present invention are 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. In any case, the reaction can be conducted with moderate heating.
  • 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. Pat. No. 4,652,416.
  • Most such materials are also commercially available; for instance, triphenyl phosphite is available from Albright and Wilson as Duraphos TPP.TM.; di-n-butyl hydrogen phosphite from Albright and Wilson as Duraphos DBHP.TM.; and triphenylthiophosphate from Ciba Specialty Chemicals as Irgalube TPPT.TM..
  • the other major component of the present composition is a hydrocarbon having ethylenic unsaturation.
  • the olefin is mono unsaturated, that is, containing only a single ethylenic double bond per molecule.
  • the olefin can be a cyclic or a linear olefin. If a linear olefin, it can be an internal olefin or an alpha-olefin.
  • the olefin can also contain aromatic unsaturation, i.e., one or more aromatic rings, provided that it also contains ethylenic (non-aromatic) unsaturation.
  • the olefin normally will contain 6 to 30 carbon atoms. Olefins having significantly fewer than 6 carbon atoms tend to be volatile liquids or gases which are not normally suitable for formulation into a composition suitable as an antiwear lubricant. Preferably the olefin will contain 6 to 18 or 6 to 12 carbon atoms, and alternatively 6 or 8 carbon atoms.
  • olefins are alkyl-substituted cyclopentenes, hexenes, cyclohexene, alkyl-substituted cyclohexenes, heptenes, cycloheptenes, alkyl-substituted cycloheptenes, octenes including diisobutylene, cyclooctenes, alkyl-substituted cyclooctenes, nonenes, decenes, undecenes, dodecenes including propylene tetramer, tridecenes, tetradecenes, pentadecenes, hexadecenes, heptadecenes, octadecenes, cyclooctadiene, norbornene, dicyclopentadiene, squalene, diphenylacetylene, and styrene.
  • 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 invention.
  • 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. Pat. 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
  • 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, 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,
  • amine salts of the above-mentioned phosphates 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, 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.
  • 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, dicresyl
  • 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.
  • alkoxylated diamines include those amine where y in the above formula is one. 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-1,3- 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, 111.
  • Such alky lenepoly amines include methylenepoly amines, 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", 2d 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 200C.
  • 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. (See carboxylic ester dispersants.) 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.
  • examples of polyhydric amines include tri-(hydroxypropyl)amine, tris-
  • 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”.
  • These extreme pressure additives can be used individually or in the form of mixtures, conveniently in an amount within the range from 0.1 to 2 parts by weight, per 100 parts by weight of the base oil. All the above can be performance enhanceded using a variety of cobase stocks, AN, AB, ADPO, ADPS, ADPM, and / or a variety of mono-basic, di-basic, and tribasic esters in conjunction with low sulfur, low aromatic, low iodine number, low bromine number, high analine point, isoparafin.
  • Blends C, D, and E are formulations showing various inventive embodiments.
  • Blends A, B, F, and G are typical commercial gas turbine engine oils for comparison.
  • inventive examples C,D, and E have superior properties in the 504 Hour 120 0 C Dry TOST sludge test compared to comparative Examples A, B, and F.
  • Example A has neither the polyol ester demulsifier nor the Mannich based dispersant.
  • Example B has the polyol ester demulsifier but not the mannich based dispersant.
  • Example F has the mannich based dispersant but not the polyol ester.
  • Example G is a typical Group I commercial gas turbine oil which provides adequate deposit control but has the drawbacks of Group I base stocks with poor emulsion characteristics.
  • Table 3 shows the benefit of adding a smaller amount of Pluronic L 121 to the inventive formulation.
  • Example I shows unexpected improvement in the sludge test compared to Example H which is identical except for the Pluronic L 121.
  • Examples C, D, and E all have favorable deposit control and emulsion characteristics. This demonstrates the importance in this embodiment, of having either a Group II or Group III base stocks or combination thereof and having both a mannich based dispersant, a polyol ester and a polyakeleyne demulsifier.

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  • Lubricants (AREA)

Abstract

Dans un mode de réalisation, l'invention porte sur une huile lubrifiante présentant une maîtrise des dépôts favorable. L'huile lubrifiante comprend une quantité majeure d'huile de base choisie dans le groupe constitué par le Groupe II, le Groupe III, GTL et toute combinaison de ceux-ci, un dispersant de type base de Mannich constituant au moins 0,1 et moins de 2,0 pour cent en poids de l'huile lubrifiante, un désémulsifiant comprenant un ester de polyol et un polyoxyalkylène, les désémulsifiants constituant au moins 0,002 à moins de 2,0 pour cent en poids de l'huile lubrifiante, l'huile lubrifiante ayant une valeur de lutte contre les dépôts inférieure à 60 mesurée à l'aide d'un test de boue TOST à sec à 120°C pendant 504 heures. Dans un deuxième mode de réalisation, l'invention porte sur un procédé de lutte contre les dépôts. Dans un troisième mode de réalisation, l'invention porte sur un procédé de formulation d'une huile pour améliorer la lutte contre les dépôts et les propriétés d'émulsion.
PCT/US2009/001983 2008-03-31 2009-03-31 Composition de lubrifiant avec une résistance au dépôt de vernis améliorée WO2009145824A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2011501849A JP2011516637A (ja) 2008-03-31 2009-03-31 改善された耐ワニス固着性の潤滑油組成物
EP09755187A EP2288681A2 (fr) 2008-03-31 2009-03-31 Composition de lubrifiant avec une résistance au dépôt de vernis améliorée
CN200980112137.3A CN101983230B (zh) 2008-03-31 2009-03-31 具有改进的抗清漆沉积性的润滑油组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7243208P 2008-03-31 2008-03-31
US61/072,432 2008-03-31

Publications (2)

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WO2009145824A2 true WO2009145824A2 (fr) 2009-12-03
WO2009145824A3 WO2009145824A3 (fr) 2010-02-25

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PCT/US2009/001983 WO2009145824A2 (fr) 2008-03-31 2009-03-31 Composition de lubrifiant avec une résistance au dépôt de vernis améliorée

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US (2) US20090253597A1 (fr)
EP (1) EP2288681A2 (fr)
JP (1) JP2011516637A (fr)
CN (1) CN101983230B (fr)
SG (1) SG188804A1 (fr)
WO (1) WO2009145824A2 (fr)

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Publication number Publication date
CN101983230A (zh) 2011-03-02
JP2011516637A (ja) 2011-05-26
WO2009145824A3 (fr) 2010-02-25
CN101983230B (zh) 2014-04-30
SG188804A1 (en) 2013-04-30
US20090247436A1 (en) 2009-10-01
US20090253597A1 (en) 2009-10-08
EP2288681A2 (fr) 2011-03-02

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