WO2008013755A2 - Compositions de lubrifiants à vitesses de désaération améliorées - Google Patents

Compositions de lubrifiants à vitesses de désaération améliorées Download PDF

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Publication number
WO2008013755A2
WO2008013755A2 PCT/US2007/016496 US2007016496W WO2008013755A2 WO 2008013755 A2 WO2008013755 A2 WO 2008013755A2 US 2007016496 W US2007016496 W US 2007016496W WO 2008013755 A2 WO2008013755 A2 WO 2008013755A2
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WIPO (PCT)
Prior art keywords
composition
lubricating
detergent
salicylate
alkyl
Prior art date
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PCT/US2007/016496
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English (en)
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WO2008013755A3 (fr
Inventor
Douglas E. Deckman
Andrew G. Horodysky
David J. Baillargeon
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Exxonmobil Research And Engineering Company
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Priority to EP07796971.5A priority Critical patent/EP2049634B1/fr
Priority to CA002658289A priority patent/CA2658289A1/fr
Publication of WO2008013755A2 publication Critical patent/WO2008013755A2/fr
Publication of WO2008013755A3 publication Critical patent/WO2008013755A3/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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • 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
    • 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
    • C10N2030/40—Low content or no 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
    • C10N2030/42—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]

Definitions

  • the invention relates to lubricant compositions exhibiting good rates of air release. More particularly, the invention relates to lubricant compositions having low ash, sulfur and phosphorous content and good rates of air release.
  • Lubricating oils including hydraulic oils and crankcase oils, often are used in environments in which the oil is subject to mechanical agitation in the presence of air. As a consequence, the air becomes entrained in the oil and also forms a foam.
  • Air entrainment generally refers to the dispersion within the oil of air bubbles less than 1 mm in diameter.
  • Air entrainment and foaming in lubricating compositions are undesirable phenomena. For example, air entrainment reduces the bulk modulus of the fluid resulting in spongy operation and poor control of a hydraulic system's response. It can result in reduced viscosity of a lubricating composition. Both air entrainment and foaming can contribute to fluid deterioration due to enhanced oil oxidation.
  • Air entrainment is more problematic than foaming. Foaming is typically depressed in lubricating compositions by the use of antifoamant additives. These additives expedite the breakup of a foam, but they do not inhibit air entrainment. Indeed, some antifoamants, such as silicone oils typically used in diesel and automotive crankcase oils, are known to retard air release. The rate of air release and amount of air entrainment of lubricating compositions may be determined by the test method of ASTM D 3427. Indeed, the rate of air release referred to herein has been determined by that method.
  • US Patent 6,090,758 discloses that foaming in a lubricant comprising a slack wax isomerate is effectively reduced by use of an antifoamant exhibiting a spreading coefficient of about 2 mN/m without increasing the air release time. While the specified antifoamant does not degrade the air release time, further improvements in enhancing air release characteristics are desirable.
  • crankcase oil to function as a hydraulic fluid to operate fuel injectors, valve train controls and the like.
  • low air entrainment and rapid air release are indicative of high performance lubricants. Indeed, it is anticipated that the rate of air release from engine lubricants will become more critical in the future to the proper operation of internal combustion engines as engine designs evolve and become ever more complex.
  • US Patent 6,713,438 discloses a lubricating oil composition that exhibits improved air release characteristics.
  • the composition comprises a basestock, typically a polyalphaolefin (PAO), and two polymers of different molecular weight.
  • PAO polyalphaolefin
  • One of the polymers is a viscoelastic fluid having a shear stress greater than 11 kPa such as a high VI PAO, and the other preferably is a block copolymer.
  • US Patent Publication No. US 2006/0116302 describes a detergent additive for lubricating oil compositions that comprises at least two of low, high and medium TBN (total base number) detergents, preferably calcium salicylate detergents. No reference is made to the air release properties of lubricants formulated with the mixed detergents. Indeed, the claimed benefits of the mixed detergents related to piston cleanliness, film forming tendency and f ⁇ ctional properties.
  • TBN total base number
  • One objective of the present invention is to provide a low ash, sulfur and phosphorous lubricating composition that exhibits good air release rates. Other objectives of the invention will become apparent from the description which follows.
  • one aspect of the invention comprises a method for improving the rate of air release of a lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of a detergent or mixture of detergents, the method comprising using as the detergent or mixture of detergents one or more salicylate detergents.
  • Another aspect of the invention is a lubricating composition
  • a lubricating composition comprising:
  • composition having less than about 0.8 wt% sulfated ash content and substantially free of a viscoelastic fluid having both a shear stress greater than 11 kPa and a kinematic viscosity greater than about 30 cSt at 100 0 C.
  • lubricating oil compositions formulated according to the invention are particularly useful as crankcase lubricants in engines wherein the lubricant provides a lubricating and a hydraulic function.
  • Shear stress measured as per SAE Paper No. 872043 (018]
  • engine oils such as gas, gasoline and diesel fueled internal combustion engine oils; however, it should be appreciated that the invention is applicable to other oils where the air release rate is an important property.
  • oils include gear oil, industrial fluids, automatic transmission fluids and the like.
  • a key advantage of the present invention is that it provides a method to enhance the air release rate of a lubricating composition by formulating the lubricating composition with one or more salicylate detergents.
  • Lubricating compositions to which the invention is applicable are especially those comprising one or more oils of lubricating viscosity selected from Group II, III, IV and V base stocks.
  • the base stock groups are defined in the American Petroleum Institute Publication "Engine Oil Licensing and Certification System," Fourteenth Edition, December 1966, Addendum 1, December 1998.
  • the base stock typically will have a viscosity of about 3 to 12, preferably 4 to 10, and more preferably 4.5 to 8 mm 2 /s (cSt) at 100 0 C.
  • Group II base stocks generally have a viscosity index (VI) of between about 80 and 120 and contain 0.03 wt% sulfur or less and 90 wt% or more saturates.
  • Group III base stocks generally have a VI greater than about 120, 0.03 wt% or less sulfur and 90 wt% or more saturates.
  • Group IV base stocks are polyalphaolefins (PAO).
  • Group V base stocks are all other base stocks not included in Groups I, II, III or IV, such as esters and alkyl aromatics.
  • a particularly suitable Group III base stock is a gas-to-liquid (GTL) base stock such as a base stock derived from a waxy hydrocarbon produced in a Fischer- Tropsch (F-T) process.
  • GTL gas-to-liquid
  • a synthesis gas comprising a mixture of H2 and CO is catalytically converted into hydrocarbons and preferably liquid hydrocarbons.
  • the mole ratio of the hydrogen to the carbon monoxide may broadly range from about 0.5 to 4, but which is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5.
  • F-T synthesis processes include processes in which the catalyst is in the form of a fixed bed, a fluidized bed or as a slurry of catalyst particles in a hydrocarbon slurry liquid.
  • the stoichiometric mole ratio for an F-T synthesis reaction is 2.0, but there are many reasons for using other than a stoichiometric ratio as those skilled in the art know.
  • the feed mole ratio of the H2 to CO is typically about 2.1/1.
  • the synthesis gas comprising a mixture of H2 and CO is bubbled up into the bottom of the slurry and reacts in the presence of the particulate F-T synthesis catalyst in the slurry liquid at conditions effective to form hydrocarbons, a portion of which are liquid at the reaction conditions and which comprise the hydrocarbon slurry liquid.
  • the synthesized hydrocarbon liquid is separated from the catalyst particles as filtrate by means such as filtration, although other separation means such as centrifugation can be used.
  • Typical conditions effective to form hydrocarbons comprising mostly C5+ paraffins, (e.g., C5+-C200) an ⁇ ⁇ preferably CiQ+ paraffins, in a slurry hydrocarbon synthesis process employing a catalyst comprising a supported cobalt component include, for example, temperatures, pressures and hourly gas space velocities in the range of from about 320-850 0 F, 80-600 psi and 100-40,000 V/hr/V, expressed as standard volumes of the gaseous CO and H2 mixture (0 0 C,
  • C5+ is used herein to refer to hydrocarbons with a carbon number of greater than 4, but does not imply that material with carbon number 5 has to be present. Similarly other ranges quoted for carbon number do not imply that hydrocarbons having the limit values of the carbon number range have to be present, or that every carbon number in the quoted range is present. It is preferred that the hydrocarbon synthesis reaction be conducted under conditions in which limited or no water gas shift reaction occurs and more preferably with no water gas shift reaction occurring during the hydrocarbon synthesis.
  • the catalyst comprises catalytically effective amounts of Co and one or more of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, preferably one which comprises one or more refractory metal oxides.
  • a suitable inorganic support material preferably one which comprises one or more refractory metal oxides.
  • Preferred supports for Co containing catalysts comprise titania.
  • Particularly useful catalysts and their preparation are known and illustrative, but nonlimiting examples may be found, for example, in U.S. Pat. Nos. 4,568,663; 4,663,305; 4,542,122; 4,621,072 and 5,545,674.
  • the waxy hydrocarbon produced in the F-T synthesis process i.e., the F-T wax, preferably has an initial boiling point in the range of from 65O 0 F to
  • a boiling range is quoted herein it defines the lower and/or upper distillation temperature used to separate the fraction. Unless specifically stated (for example, by specifying that the fraction boils continuously or constitutes the entire range) the specification of a boiling range does not require any material at the specified limit has to be present, rather it excludes material boiling outside that range.
  • the waxy feed preferably comprises the entire 650-750°F+ fraction formed by the hydrocarbon synthesis process, having an initial cut point between 650 0 F and 750 0 F determined by the practitioner and an end point, preferably above 1050 0 F, determined by the catalyst and process variables employed by the practitioner for the synthesis.
  • Such fractions are referred to herein as "650-750°F+ fraction formed by the hydrocarbon synthesis process, having an initial cut point between 650 0 F and 750 0 F determined by the practitioner and an end point, preferably above 1050 0 F, determined by the catalyst and process variables employed by the practitioner for the synthesis.
  • Such fractions are referred to herein as "650-
  • Waxy feeds may be processed as the entire fraction or as subsets of the entire fraction prepared by distillation or other separation techniques.
  • the waxy feed also typically comprises more than 90%, generally more than 95% and preferably more than 98 wt% paraffinic hydrocarbons, most of which are normal paraffins.
  • Waxy feeds having these properties and useful in the process of the invention have been made using a slurry F-T process with a catalyst having a catalytic cobalt component, as previously indicated.
  • the process of making the lubricating base oil from the F-T wax may be characterized as a hydrodewaxing process. This process may be operated in the presence of hydrogen, and hydrogen partial pressures range from about 600 to 6000 kPa.
  • the ratio of hydrogen to the hydrocarbon feedstock typically range from about 10 to 3500 n.l.l.-l (56 to 19,660 SCF/bbl) and the space velocity of the feedstock typically ranges from about 0.1 to 20 LHSV, preferably 0.1 to 10 LHSV.
  • Hydrodewaxing catalysts useful in the conversion of the n-paraffin waxy feedstocks disclosed herein to form the isoparaffinic hydrocarbon base oil are zeolite catalysts, such as ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM- 12, ZSM-38, ZSM-48, offretite, ferrierite, zeolite beta, zeolite theta, and zeolite alpha, as disclosed in USP 4,906,350. These catalysts are used in combination with Group VItI metals, in particular palladium or platinum. The Group VIII metals may be incorporated into the zeolite catalysts by conventional techniques, such as ion exchange.
  • conversion of the waxy feedstock may be conducted over a combination of Pt/zeolite beta and Pt/ZSM-23 catalysts in the presence of hydrogen.
  • the process of producing the lubricant oil base stocks comprises hydroisomerization and dewaxing over a single catalyst, such as Pt/ZSM-35.
  • the waxy feed can be fed over Group VIII metal loaded ZSM-48, preferably Group VIII noble metal loaded ZSM-48, more preferably Pt/ZSM-48 in either one stage or two stages. In any case, useful hydrocarbon base oil products may be obtained. Catalyst ZSM-48 is described in USP 5,075,269.
  • a dewaxing step when needed, may be accomplished using either well known solvent or catalytic dewaxing processes and either the entire hydro- isomerate or the 650-75O 0 F+ fraction may be dewaxed, depending on the intended use of the 650-750 0 F- material present, if it has not been separated from the higher boiling material prior to the dewaxing.
  • the hydroisomerate may be contacted with chilled solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK/MIBK, or mixtures of MEK/toluene and the like, and further chilled to precipitate out the higher pour point material as a waxy solid which is then separated from the solvent-containing lube oil fraction which is the raff ⁇ nate.
  • the raf ⁇ nate is typically further chilled in scraped surface chillers to remove more wax solids.
  • Low molecular weight hydrocarbons such as propane are also used for dewaxing, in which the hydroisomerate is mixed with liquid propane, a least a portion of which is flashed off to chill down the hydroisomerate to precipitate out the wax.
  • the wax is separated from the raffinate by filtration, membrane separation or centrifugation.
  • the solvent is then stripped out of the raffinate, which is then fractionated to produce the preferred base stocks useful in the present invention.
  • catalytic dewaxing in which the hydroisomerate is reacted with hydrogen in the presence of a suitable dewaxing catalyst at conditions effective to lower the pour point of the hydroisomerate.
  • Catalytic dewaxing also converts a portion of the hydroisomerate to lower boiling materials, in the boiling range, for example, 650-750 0 F-, which are separated from the heavier 650-750°F+ base stock fraction and the base stock fraction fractionated into two or more base stocks. Separation of the lower boiling material may be accomplished either prior to or during fractionation of the 650-750°F+ material into the desired base stocks.
  • Any dewaxing catalyst which will reduce the pour point of the hydroisomerate and preferably those which provide a large yield of lube oil base stock from the hydroisomerate may be used.
  • shape selective molecular sieves which, when combined with at least one catalytic metal component, have been demonstrated as useful for dewaxing petroleum oil fractions and include, for example, ferrierite, mordenite, ZSM-5, ZSM-I l, ZSM-23, ZSM-35, ZSM-22 also known as theta one or TON, and the silicoaluminophosphates known as SAPO's.
  • a dewaxing catalyst which has been found to be unexpectedly particularly effective comprises a noble metal, preferably Pt, composited with H-mordenite. The dewaxing may be accomplished with the catalyst in a fixed, fluid or slurry bed.
  • Typical dewaxing conditions include a temperature in the range of from about 400-600 0 F, a pressure of 500-900 psig, H2 treat rate of 1500-3500 SCF/B for flow-through reactors and LHSV of 0.1-10, preferably 0.2-2.0.
  • the dewaxing is typically conducted to convert no more than 40 wt% and preferably no more than 30 wt% of the hydroisomerate having an initial boiling point in the range of 650-750 0 F to material boiling below its initial boiling point.
  • the GTL base stock suitable for use in the invention will have a kinematic viscosity in the range of about 2 to 50 mm ⁇ /s at 100 0 C and preferably in the range of about 3.5 to 30 mm 2 /s at 100 0 C and a VI greater than about 130, preferably greater than 135 and more preferably 140 or greater.
  • the GTL base stock of the invention is further characterized as having a pour point of -5°C or lower, preferably about -10 0 C or lower and under some conditions advantageously having pour points of about -25°C to about -40 0 C.
  • a preferred GTL base stock is one comprising paraffinic hydrocarbon components in which the extent of branching, as measured by the percentage of methyl hydrogens (BI), and the proximity of branching, as measured by the percentage of recurring methylene carbons which are four or more carbons removed from an end group or branch (CH2 > 4), are such that: (a) BI-0.5(CH2 > 4) >15; and (b) BI+0.85(CH2 > 4) ⁇ 45 as measured over said liquid hydrocarbon composition as a whole.
  • the preferred GTL base stock can be further characterized, if necessary, as having less than 0.1 wt% aromatic hydrocarbons, less than 20 wppm nitrogen containing compounds, less than 20 wppm sulfur containing compounds, a pour point of less than -18°C, preferably less than -30 0 C, a preferred BI > 25.4 and (CH2 > 4) ⁇ 22.5. They have a nominal boiling point of
  • 370 0 C + on average they average fewer than 10 hexyl or longer branches per 100 carbon atoms and on average have more than 16 methyl branches per 100 carbon atoms. They also can be characterized by a combination of dynamic viscosity, as measured by CCS at -40 0 C, and kinematic viscosity, as measured at 100 0 C represented by the formula: DV (at -40 0 C) ⁇ 2900 (KV @ 100 0 C) - 7000.
  • the preferred GTL base stock is also characterized as comprising a mixture of branched paraffins characterized in that the lubricant base oil contains at least 90% of a mixture of branched paraffins, wherein said branched paraffins are paraffins having a carbon chain length of about C20 to about C40, a molecular weight of about 280 to about 562, a boiling range of about 650 0 F to about 1050 0 F, and wherein said branched paraffins contain up to four alkyl branches and wherein the free carbon index of said branched paraffins is at least about 3.
  • Branching Index BI
  • CH2 > 4 Branching Proximity
  • FCI Free Carbon Index
  • H atom types are defined according to the following regions:
  • the branching index (BI) is calculated as the ratio in percent of non- benzylic methyl hydrogens in the range of 0.5 to 1.05 ppm, to the total non- benzylic aliphatic hydrogens in the range of 0.5 to 2.1 ppm.
  • a 90.5 MHz 3 CMR single pulse and 135 Distortionless Enhancement by Polarization Transfer (DEPT) NMR spectra are obtained on a Brucker 360 MHzAMX spectrometer using 10% solutions in CDCL3. TMS is the internal chemical shift reference. CDCL3 solvent gives a triplet located at 77.23 ppm in the 13c spectrum. All single pulse spectra are obtained under quantitative conditions using 45 degree pulses (6.3 ⁇ s), a pulse delay time of 60 s, which is at least five times the longest carbon spin-lattice relaxation time (Tj), to ensure complete relaxation of the sample, 200 scans to ensure good signal-to-noise ratios, and WALTZ- 16 proton decoupling.
  • Tj longest carbon spin-lattice relaxation time
  • "29.8 ppm is due to equivalent recurring methylene carbons which are four or more removed from an end group or branch (CH2 > 4).
  • the types of branches are determined based primarily on the ⁇ 3 C chemical shifts for the methyl carbon at the end of the branch or the methylene carbon one removed from the methyl on the branch.
  • FCI Free Carbon Index
  • a calculate the average carbon number of the molecules in the sample which is accomplished with sufficient accuracy for lubricating oil materials by simply dividing the molecular weight of the sample oil by 14 (the formula weight of CH2); b. divide the total carbon- 13 integral area (chart divisions or area counts) by the average carbon number from step a. to obtain the integral area per carbon in the sample; c. measure the area between 29.9 ppm and 29.6 ppm in the sample; and d. divide by the integral area per carbon from step b. to obtain FCI.
  • Branching measurements can be performed using any Fourier Transform NMR spectrometer.
  • the measurements are performed using a spectrometer having a magnet of 7.0T or greater.
  • the spectral width was limited to the saturated carbon region, about 0-80 ppm vs. TMS (tetramethylsilane).
  • Solutions of 15-25 percent by weight in chloroform-dl were excited by 45 degrees pulses followed by a 0.8 sec acquisition time.
  • the proton decoupler was gated off during a 10 sec delay prior to the excitation pulse and on during acquisition. Total experiment times ranged from 11-80 minutes.
  • the DEPT and APT sequences were carried out according to literature descriptions with minor deviations described in the Varian or Bruker operating manuals.
  • DEPT Distortionless Enhancement by Polarization Transfer. DEPT does not show quaternaries.
  • the DEPT 45 sequence gives a signal for all carbons bonded to protons.
  • DEPT 90 shows CH carbons only.
  • DEPT 135 shows CH and CH3 up and CH2 180 degrees out of phase (down).
  • APT is Attached Proton Test. It allows all carbons to be seen, but if CH and CH3 are up, then quaternaries and CH2 are down.
  • the sequences are useful in that every branch methyl should have a corresponding CH. And the methyls are clearly identified by chemical shift and phase.
  • the branching properties of each sample are determined by C- 13 NMR using the assumption in the calculations that the entire sample is isoparaffinic.
  • Suitable polyalphaolefins (PAOs) for use in compositions of the invention comprise relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins such as C2 to C32 alphaolefins with Cg to Cj6 alphaolefins being preferred.
  • PAO base stocks are conveniently made by the polymerization of alphaolefins in the presence of a polymerization catalyst such as the Friedel- Crafts catalysts.
  • a polymerization catalyst such as the Friedel- Crafts catalysts.
  • PAO synthesis can be found in US 3,742,082; US 3,769,363; US 4,413,156; US 4,434,408; US 4,910,355; and US 4,956,122 to mention a few.
  • a lubricating composition of the invention comprises a major amount of an oil of lubricating viscosity and especially one or more oils selected from Group II, Group III (including GTL), Group IV and Group V base stocks.
  • major amount is meant greater than 50 wt%, conveniently between 75 wt% to 90 wt% and preferably between 65 wt% to 80 wt%, based on the total weight of the lubricating composition.
  • the mixture will comprise Group III and Group IV base stocks.
  • the air release rate of a lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of a detergent can be improved by using as the detergent one or more salicylate detergents.
  • suitable salicylate detergents include sulfur-free salicylate detergents, such as alkali and alkaline earth metal salts of alkyl salicylic acid and ashless salicylate detergents such as amides and esters of alkyl salicylic acid.
  • the alkylsalicylic acid will have one or more alkyl groups of at least 8 carbon atoms in the alkyl groups with 10 to 20 carbon atoms often being preferred.
  • the alkyl groups of the amide will have from about 2 to about 50 carbon atoms and preferably 8 to 20 carbon atoms.
  • the esters of alkyl salicylic acid will be formed from alcohols having about 4 to about 20 carbon atoms and preferably 6 to 12 carbon atoms. These detergents may be neutral or overbased or mixtures thereof. Borated salicylate detergents may also be used.
  • the salicylate detergent constitutes the sole detergent in the composition.
  • the detergent is an alkaline earth metal salicylate and mixtures of calcium and magnesium salicylate or mixtures of calcium and magnesium salicylates, especially a calcium and magnesium salicylate.
  • the detergent comprises three calcium salicylate detergents, one with a 270 TBN, another with a 170 TBN and yet another with a 70 TBN.
  • the composition according to this preferred embodiment would comprise each of the detergents in an amount of about 0.1 wt% to about 2 wt%, based on the total weight of the lubricating composition.
  • the salicylate detergent(s) will typically be used in an amount sufficient to provide the composition with a TBN in the range of about 4 to 8 and preferably about 5 to 7.
  • the composition will comprise about 1 wt% to about 6 wt% and preferably 1 wt% to 3 wt% salicylate detergent(s) based on the total weight of the composition.
  • the instant invention can be used with additional lubricant components in effective amounts typically used in lubricant compositions such as alkyl- aromatic lubricant oils, and performance additives such as, for example but not limited to, oxidation inhibitors, corrosion and rust inhibitors, metal deactivators, antiwear agents, extreme pressure additives, pour point depressants, wax modifiers, viscosity modifiers, lubricating agents, defoamants, demulsifiers and others.
  • performance additives such as, for example but not limited to, oxidation inhibitors, corrosion and rust inhibitors, metal deactivators, antiwear agents, extreme pressure additives, pour point depressants, wax modifiers, viscosity modifiers, lubricating agents, defoamants, demulsifiers and others.
  • Suitable antioxidants include aminic antioxidants and phenolic antioxidants.
  • Typical aminic antioxidants include alkylated aromatic amines, especially those in which the alkyl group contains no more than 14 carbon atoms.
  • Typical phenolic antioxidants include derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p- position to each other and which contain alkyl substituents. Mixtures of phenolic and aminic antioxidants also may be used.
  • Such additives may be used in an amount of about 0.02 to 5 wt%, and preferably about 0.1 wt% to about 2 wt% based on the total weight of the composition.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and aminic alkyl sulfonic acids may be used.
  • Corrosion inhibitors that may be used include benzotriazoles, tolyltriazoles and their derivatives.
  • Suitable dispersants include succinimide dispersants, ester dispersants, ester-amide dispersants, and the like.
  • the dispersant is a succinimide dispersant, especially a polybutenyl succinimide.
  • the molecular weight of the polybutenyl group may range from about 800 to about 4000 or more and preferably from about 1300 to about 2500.
  • the dispersant may be head capped or borated or both.
  • a commonly used class of antiwear additives is zinc dialkyldithio- phosphates in which the alkyl groups typically have from 3 to about 18 carbon atoms with 3 to 10 carbon atoms being preferred.
  • Suitable antifoam additives include silicone oils or polysil ⁇ xane oils usually used in amounts of from 0.0001 to 0.01 wt% active ingredient.
  • Pour point depressants are well known lubricant additives. Typical examples are dialkylfumarates, polyalkylmethacrylates, and the like.
  • the number and types of friction modifiers are voluminous. In general, they include metal salts of fatty acids, glycerol esters and alkoxylated fatty amines to mention a few.
  • VI improver such as linear or radial styrene-isoprene VI improvers, olefin copolymers, polymethacrylates, and the like.
  • VI improvers such as linear or radial styrene-isoprene VI improvers, olefin copolymers, polymethacrylates, and the like.
  • the various lubricant additives will comprise from about 0.5 wt% to about 25 wt% and preferably from about 2 wt% to about 10 wt% based on the total weight of the composition except where otherwise specified herein.
  • the composition of the invention is substantially free of added viscoelastic fluids that have both a shear stress greater than 11 kPa and a kinematic viscosity greater than 30 cSt at
  • composition 100 0 C. Any amount of such material that does not affect the air release rate of the composition may be present; however, it is preferred that the composition be totally free of such material.
  • a series of multigrade, internal combustion, engine oils were prepared according to the formulations show in Table 1, in which PAO 6 is a polyalpha- olefin basestock with a KV at 100 0 C of 5.8 cSt. Different detergents were used in quantities providing engine oils with a TBN of 7. Each of the blends contained the same polybutenylsuccinimide dispersant zinc dialkyldithio- phosphate antiwear additive, ashless antioxidant, silicone defoamant, friction modifier and VI improving compounds in the same amounts (i.e., 15.47 wt% of the total composition). Additionally, a reference blend without detergent, but containing all other additives in the same amounts was prepared. All of the blends were tested for air release rate according to ASTM D 3427. The results are shown graphically in the accompanying figure. As can be seen, salicylate detergents provide a significant performance benefit by quickly releasing entrained air.

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

Abstract

La vitesse de désaération de compositions lubrifiantes est notablement améliorée lorsque la composition est formulée avec des détergents salicylate alkyle, notamment des détergents salicylate alkyle de calcium ou de magnésium. Des compositions présentant les vitesses de désaération améliorées sont sensiblement exemptes de fluide viscoélastique dont la contrainte de cisaillement est supérieure à 11 kPa et la viscosité dépasse 30 cSt à 100°C.
PCT/US2007/016496 2006-07-28 2007-07-20 Compositions de lubrifiants à vitesses de désaération améliorées WO2008013755A2 (fr)

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EP07796971.5A EP2049634B1 (fr) 2006-07-28 2007-07-20 Amélioration des taux de désaération de compositions lubrifiantes
CA002658289A CA2658289A1 (fr) 2006-07-28 2007-07-20 Compositions de lubrifiants a vitesses de desaeration ameliorees

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US83387206P 2006-07-28 2006-07-28
US60/833,872 2006-07-28

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EP3153569B1 (fr) * 2015-10-08 2018-07-04 Infineum International Limited Méthode de lubrification et l'utilisation de lubrifiant

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DE102009034983A1 (de) * 2008-09-11 2010-04-29 Infineum International Ltd., Abingdon Verfahren zum Vermindern von Asphaltenablagerung in einem Motor
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US20170056575A1 (en) * 2015-08-27 2017-03-02 Cook Medical Technologies Llc Dialysis catheter and methods of use thereof
US10597600B2 (en) * 2016-03-24 2020-03-24 Shell Oil Company Lubricating oil composition
CN113999716B (zh) * 2020-07-28 2023-04-07 中国石油天然气股份有限公司 一种润滑油组合物及其应用

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EP3153569B1 (fr) * 2015-10-08 2018-07-04 Infineum International Limited Méthode de lubrification et l'utilisation de lubrifiant
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US20080026971A1 (en) 2008-01-31
CA2658289A1 (fr) 2008-01-31
EP2049634A2 (fr) 2009-04-22
WO2008013755A3 (fr) 2008-03-20
EP2049634B1 (fr) 2018-09-19

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