EP0874040B1 - Synergistische Organomolybdänumzusammensetzungen und Schmiermittelzusammensetzungen die diese enthalten - Google Patents

Synergistische Organomolybdänumzusammensetzungen und Schmiermittelzusammensetzungen die diese enthalten Download PDF

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EP0874040B1
EP0874040B1 EP97106614A EP97106614A EP0874040B1 EP 0874040 B1 EP0874040 B1 EP 0874040B1 EP 97106614 A EP97106614 A EP 97106614A EP 97106614 A EP97106614 A EP 97106614A EP 0874040 B1 EP0874040 B1 EP 0874040B1
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Prior art keywords
molybdenum
complex
carbon atoms
formula
alkyl groups
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French (fr)
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EP0874040A1 (de
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Thomas J. Karol
Steven G. Donnelly
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Vanderbilt Chemicals LLC
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RT Vanderbilt Co Inc
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Priority to DE69714213T priority Critical patent/DE69714213T2/de
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Priority to CA002235182A priority patent/CA2235182C/en
Priority to JP10146464A priority patent/JP3090904B2/ja
Priority to CN98101624A priority patent/CN1098348C/zh
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    • C10M163/00Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
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    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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    • C10M2219/068Thiocarbamate metal salts
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    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108Phenothiazine
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/045Metal containing thio derivatives
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
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    • C10M2227/00Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09Complexes with metals
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    • C10N2010/02Groups 1 or 11
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Definitions

  • the invention concerns lubricating compositions having improved properties. Another aspect of the invention relates to additive compositions which impart antiwear and antiscuffing properties to lubricating compositions used for internal combustion engines such as gasoline engine and diesel engine.
  • additives known as antiwear agents are employed to increase the load carrying capacity of lubricants.
  • the antiwear agents promote the formation of a surface film and thereby prevent wear of the contacting surfaces.
  • the mechanical efficiency enhanced by decreased friction loss further results in decreased fuel consumption and energy savings.
  • WO 95/15368 describes a lubricating oil composition
  • a lubricating oil composition comprising a base stock oil and (a) oxymolybdenum monoglyceride or oxymolybdenum diethylate amide and (b) a metal dithiocarbamate.
  • the lubricating composition is described as exhibiting improved wear resistance and copper corrosiveness and a low coefficient of friction.
  • US 5,364,545 describes a lubricating oil composition
  • a lubricating oil composition comprising (a) a lubricating oil basestock, (b) an organomolybdenum compound and (c) a zinc dithiophosphate salt or a zinc dithiocarbamate salt.
  • the lubricating oil compositions are described to have a low coefficient of friction and reduced copper corrosion.
  • synergistic antiwear compositions comprising:
  • compositions having improved lubricating properties and comprising a major portion of an oil of lubricating viscosity and 0.1 to 10.0 percent by weight of a composition comprising (1) an organomolybdenum complex prepared by reacting about 1 mole fatty oil, 1.0 to 2.5 moles diethanolamine and a molybdenum source sufficient to yield 0.1 to 12.0 percent of molybdenum based on the weight of the complex and (2) a sulfur compound of the 5 formula I, II, or V.
  • the organomolybdenum component of the invention is prepared by sequentially reacting fatty oil, diethanolamine and a molybdenum source by the condensation method described in U.S. Pat. No. 4,889,647. The reaction yields a reaction product mixture.
  • the major components are believed to have the structural formulae wherein R represents a fatty oil residue.
  • the preferred fatty oils are glyceryl esters of higher fatty acids containing at least 12 carbon atoms and may contain 22 carbon atoms and higher. Such esters are commonly known as vegetable and animal oils. Vegetable oils particularly useful are oils derived from coconut, corn, cottonseed, linseed, peanut, soybean and sunflower seed. Similarly, animal fatty oils such as tallow may be used.
  • the source of molybdenum is an oxygen-containing molybdenum compound capable of reacting with the intermediate reaction product of fatty oil and diethanolamine to form an ester-type molybdenum complex.
  • the source of molybdenum includes, among others, ammonium molybdates, molybdenum oxides and mixtures thereof.
  • 1,3,4-thiadiazoles of formula I may be prepared by the method disclosed in U.S. Pat. No. 4,761, 482 and U.S. Pat. No. 4,880,437.
  • Terpene residues are preferably derived from pinene and limonene having the structural formulae given hereinbelow.
  • the alkyl groups represented by R and R 1 contain preferably 1 to 22 carbon atoms and may be branched or straight chain. Particularly preferred are compounds wherein both alkyl groups together contain a total of at least 22 carbon atoms.
  • Groups R 2 and R 3 in the formula I represent branched or straight chain alkyl groups containing 1 to 22 carbon atoms and cyclic aliphatic groups such as cyclohexyl, cyclopentyl and cycloheptyl.
  • the bisdithiocarbamates of formula II are known compounds described in U.S. Pat. No. 4,648,985.
  • the compounds are characterized by groups R 4 to R 7 which are the same or different and are hydrocarbyl groups having 1 to 13 carbon atoms.
  • the group R 8 is an aliphatic group such as straight and branched alkylene groups containing 1 to 8 carbons.
  • Particularly preferred is methylenebis (dibutyldithiocarbamate) available commercially under the tradename VANLUBE® 7723 from R.T. Vanderbilt Company, Inc.
  • the phosphorodithioate esters of the formula V are known compounds.
  • One of the processes of manufacture is disclosed in U.S. Pat. No. 3,567,638
  • Groups R 4 and R 5 in the formula V may be the same or different and may be selected from branched and straight chain alkyl groups. Preferred are groups containing 1 to 8 carbon atoms.
  • the sulfur compounds are known to possess certain lubricating properties such as oxidation, wear and corrosion inhibition in various lubricating media. Sometimes, however, the sulfur compounds alone do not provide adequate antiwear protection for the varied heavy duty applications of many industrial and automotive lubricants.
  • the high concentrations of sulfur compounds may produce an adverse effect on the overall performance of the lubricant.
  • the above sulfur compounds produce synergistic antiwear effect when combined with organomolybdenum compounds in certain ratios.
  • Synergism is displayed by compositions containing 1 to 5 parts by weight of the sulfur compound to 5 to 1 part by weight of the molybdenum compound.
  • compositions possess good antioxidant properties. Even in instances where the sulfur compounds do not possess an antioxidant activity, the combination with the molybdenum complexes provides a composition with good overall antioxidant properties.
  • the synergistic compositions may be incorporated in any lubricating media by known methods.
  • the compositions impart antiwear as well as oxidation inhibiting and extreme pressure properties to natural and synthetic lubricants formulated as oils or greases.
  • the base oils employed as lubricant vehicles are typical natural and synthetic oils used in automotive and industrial applications such as, among others, turbine oils, hydraulic oils, gear oils, crankcase oils and diesel oils.
  • Natural base oils include mineral oils, petroleum oil, paraffinic oils and the ecologically desirable vegetable oils.
  • Typical synthetic oils include pentaerythritol esters, poly-alpha-olefins, hydrogenated mineral oils, silicones and silanes.
  • compositions of the invention may be incorporated in the lubricant in an amount effective to produce the desired antiwear characteristics.
  • An amount from 0.1 to 10.0 percent will be sufficient for most applications.
  • a preferred range is from 0.5 to 3. 0 percent by weight of the total lubricant composition.
  • the lubricating compositions may contain other conventional additives depending on the intended use of the lubricant.
  • formulations may contain rust inhibitors such as metal salts of alkylnaphthalenesulfonic acids, demulsifiers, dispersants, detergents and supplemental antioxidants, particularly alkylated diphenylamines.
  • the grease formulations may contain various thickening agents such as, among others, silicate minerals, metal soaps and organic polymers.
  • the test was performed with a molybdenum complex in conjunction with the following ashless sulfur compound synergists of the invention: S-dicarbobutoxyethyl 0,0-dipropylphosphorodithioate (hereinafter phosphorodithioate ester) and methylenebis-(dibutyldithiocarbamate).
  • the molybdenum complex was a reaction product of coconut oil, 2,2'-iminobisethanol and hexammonium salt of molybdic acid.
  • the base oil was a hydrofinished naphthenic oil (ISO VG 22 manufactured by Sun Refining and Marketing Co.).
  • the modified Falex Wear Test described in Example 1 was performed with the same molybdenum complex in conjunction with the following metal salts of the sulfur compound synergists: nickel dilauryldithiocarbamate, calcium di-2-ethylhexyldithiophosphate, aluminum di-2-ethylhexyldithiophosphate, tellurium di-2-ethylhexyldithiophosphate, and C 12-14 -alkylamine salt of tert-octyl phosphates (hereinafter dithiophosphate amine salt).
  • the base oil was a hydrofinished naphthenic oil (ISO VG 22).
  • a thin film oxygen uptake test was conducted essentially according to the method described by Chia-Soon Ju et al, J. Am. Soc. Lubricating Eng., 40, 2, 75-83, 1984.
  • the oxidation induction time of the lubricant was measured under conditions which simulate the high temperature oxidation processes in automotive engines by modified rotary bomb oxidation test method ASTM D-2272.
  • the test was conducted with 1.5 gram samples of hydrofinished naphthenic oil, ISO VG 22.
  • the composition of the invention described in Example 1 and, for comparison, the individual components, were added to the oil in the amount indicated in Table III.
  • the test was conducted at 160°C and initial oxygen pressure of 620.6 kPa (90 psi).
  • a "pass" oil has a high induction time, while a “fail” oil has a low induction time.
  • the compositions of the invention display good antioxidative effect as demonstrated by the data compiled in Table III.

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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)

Claims (7)

  1. Synergistische Verschleißschutzzusammensetzung, die aus
    a) einem molybdänorganischen Komplex, der durch Umsetzung von etwa 1 mol Fettöl, 1,0 bis 2,5 mol Diethanolamin und einer Molybdänquelle hergestellt ist, die ausreicht, 0,1 bis 12,0 % Molybdän, bezogen auf das Gewicht des Komplexes, zu ergeben, und
    b) einer organischen Schwefelverbindung besteht, die aus der Gruppe ausgewählt ist, die aus 1,3,4-Thiadiazolverbindungen mit der Formel
    Figure 00130001
    besteht, worin R und R1 unabhängig voneinander aus Alkylgruppen mit 1 bis 22 Kohlenstoffatomen, dem Terpenrest und dem Maleinsäurerest mit der Formel
    Figure 00130002
    ausgewählt sind, R2 und R3 C1- bis C22-Alkyl- und C5- bis C7-Cycloalkylgruppen bedeuten und entweder R2 oder R3 und, wenn R2 und R3 C9- bis C22-Alkylgruppen bedeuten, entweder R oder R1 Wasserstoff bedeuten können,
    wobei das Verhältnis von Molybdänkomplex zu Schwefel 1 : 5 bis 5 : 1 beträgt.
  2. Zusammensetzung nach Anspruch 1, worin die 1,3,4-Thiadiazolverbindung 2,5-Bis(2-pinanylthio)-1,3,4-thiadiazol ist.
  3. Synergistische Verschleißschutzzusammensetzung, die aus
    a) einem molybdänorganischen Komplex, der durch Umsetzung von etwa 1 mol Fettöl, 1,0 bis 2,5 mol Diethanolamin und einer Molybdänquelle hergestellt ist, die ausreicht, 0,1 bis 12,0 % Molybdän, bezogen auf das Gewicht des Komplexes, zu ergeben, und
    b) einer Bisdithiocarbamatverbindung mit der Formel
    Figure 00140001
    worin R4, R5, R6 und R7 aliphatische Kohlenwasserstoffgruppen mit 1 bis 13 Kohlenstoffatomen bedeuten und R8 eine Alkylengruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, besteht,
    wobei das Verhältnis von Molybdänkomplex zu Bisdithiocarbamat 1 : 5 bis 5 : 1 beträgt.
  4. Zusammensetzung nach Anspruch 3, worin die Bisdithiocarbamatverbindung Methylenbis(dibutyldithiocarbamat) ist.
  5. Synergistische Verschleißschutzzusammensetzung, die aus
    a) einem molybdänorganischen Komplex, der durch Umsetzung von etwa 1 mol Fettöl, 1,0 bis 2,5 mol Diethanolamin und einer Molybdänquelle hergestellt ist, die ausreicht, 0,1 bis 12,0 % Molybdän, bezogen auf das Gewicht des Komplexes, zu ergeben, und
    b) einem Phosphorodithioatester mit der Formel
    Figure 00150001
    worin R4 und R5 gegebenenfalls voneinander verschieden sein können und aus Alkylgruppen mit 1 bis 8 Kohlenstoffatomen ausgewählt sind,
    wobei das Verhältnis von Molybdänkomplex zu Schwefel 1 : 5 bis 5 : 1 beträgt.
  6. Zusammensetzung nach Anspruch 5, worin der Ester S-Dicarbobutoxyethyl-0,0-dipropylphosphorodithioat ist.
  7. Schmiermittelzusammensetzung, die ein Öl mit Schmierviskosität und 0,1 bis 10,0 Gew.% einer synergistischen Verschleißschutzzusammensetzung umfaßt, die aus
    a) einem molybdänorganischen Komplex, der durch Umsetzung von etwa 1 mol Fettöl, 1,0 bis 2,5 mol Diethanolamin und einer Molybdänquelle hergestellt ist, die ausreicht, 0,1 bis 12,0 % Molybdän, bezogen auf das Gewicht des Komplexes, zu ergeben, und
    b) einer organischen Schwefelverbindung besteht, die aus der Gruppe ausgewählt ist, die aus
    I) 1,3,4-Thiadiazolverbindungen mit der Formel
    Figure 00160001
    worin R und R1 unabhängig voneinander aus Alkylgruppen mit 1 bis 22 Kohlenstoffatomen, dem Terpenrest und dem Maleinsäurerest mit der Formel
    Figure 00160002
    ausgewählt sind, R2 und R3 C1- bis C22-Alkylund C5- bis C7-Cycloalkylgruppen bedeuten und entweder R2 oder R3 und, wenn R2 und R3 C9- bis C22-Alkylgruppen bedeuten, entweder R oder R1 Wasserstoff bedeuten können,
    II) Bisdithiocarbamatverbindungen mit der Formel
    Figure 00170001
    worin R4, R5, R6 und R7 aliphatische Kohlenwasserstoffgruppen mit 1 bis 13 Kohlenstoffatomen bedeuten und R8 eine Alkylengruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, und
    III) Phosphorodithioatestern mit der Formel
    Figure 00170002
    worin R4 und R5 gegebenenfalls voneinander verschieden sein können und aus Alkylgruppen mit 1 bis 8 Kohlenstoffatomen ausgewählt sind, besteht,
    wobei das Verhältnis von Molybdänkomplex zu Schwefelverbindung 1 : 5 bis 5 : 1 beträgt.
EP97106614A 1997-04-22 1997-04-22 Synergistische Organomolybdänumzusammensetzungen und Schmiermittelzusammensetzungen die diese enthalten Expired - Lifetime EP0874040B1 (de)

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DE69714213T DE69714213T2 (de) 1997-04-22 1997-04-22 Synergistische Organomolybdänumzusammensetzungen und Schmiermittelzusammensetzungen die diese enthalten
EP97106614A EP0874040B1 (de) 1997-04-22 1997-04-22 Synergistische Organomolybdänumzusammensetzungen und Schmiermittelzusammensetzungen die diese enthalten
CA002235182A CA2235182C (en) 1997-04-22 1998-04-20 Synergistic organomolybdenum compositions and lubricating compositions containing same
JP10146464A JP3090904B2 (ja) 1997-04-22 1998-04-21 相乗的耐摩耗組成物及びこの組成物を含有する潤滑組成物
CN98101624A CN1098348C (zh) 1997-04-22 1998-04-22 协合有机钼组合物和含有它的润滑组合物

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WO2000055284A1 (en) * 1999-03-15 2000-09-21 Shell Internationale Research Maatschappij B.V. Grease composition for constant velocity joints
WO2003027215A2 (en) * 2001-09-21 2003-04-03 R.T. Vanderbilt Company, Inc. Improved antioxydant additive compositions and lubricating compositions containing the same
US7112558B2 (en) 2002-02-08 2006-09-26 Afton Chemical Intangibles Llc Lubricant composition containing phosphorous, molybdenum, and hydroxy-substituted dithiocarbamates
US6562765B1 (en) * 2002-07-11 2003-05-13 Chevron Oronite Company Llc Oil compositions having improved fuel economy employing synergistic organomolybdenum components and methods for their use
WO2004033605A2 (en) * 2002-10-04 2004-04-22 R.T. Vanderbilt Company, Inc. Synergistic organoborate compositions and lubricating compositions containing same
US20100152073A1 (en) 2008-12-17 2010-06-17 Chevron Oronite Company Llc Lubricating oil compositions
JP2010285475A (ja) * 2009-06-09 2010-12-24 Yushiro Chem Ind Co Ltd 潤滑油組成物
FR2961823B1 (fr) * 2010-06-25 2013-06-14 Total Raffinage Marketing Compositions lubrifiantes pour transmissions automobiles
DE112011103822T5 (de) 2010-11-19 2013-08-22 Chevron U.S.A. Inc. Schmiermittel für Schlagwerkausrüstung
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DE69714213T2 (de) 2003-02-20
CN1098348C (zh) 2003-01-08
CA2235182C (en) 2004-08-10
EP0874040A1 (de) 1998-10-28
CN1201066A (zh) 1998-12-09
CA2235182A1 (en) 1998-10-22
JP3090904B2 (ja) 2000-09-25
JPH1143686A (ja) 1999-02-16

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