EP1280873A1 - Antioxidantzusatzstoffzusammensetzung für schmieröle - Google Patents

Antioxidantzusatzstoffzusammensetzung für schmieröle

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Publication number
EP1280873A1
EP1280873A1 EP01918980A EP01918980A EP1280873A1 EP 1280873 A1 EP1280873 A1 EP 1280873A1 EP 01918980 A EP01918980 A EP 01918980A EP 01918980 A EP01918980 A EP 01918980A EP 1280873 A1 EP1280873 A1 EP 1280873A1
Authority
EP
European Patent Office
Prior art keywords
compound
composition
cst
phenolic
aminic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01918980A
Other languages
English (en)
French (fr)
Inventor
Jason Gao
Christopher John May
Jeffrey Robert Torkelson
Paul S. Woolley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1280873A1 publication Critical patent/EP1280873A1/de
Withdrawn legal-status Critical Current

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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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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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    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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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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    • C10N2010/12Groups 6 or 16
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    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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Definitions

  • This invention relates to lubricating oil compositions, especially lubricants used in internal combustion engines, comprising base oils high in saturates which are resistant to oxidation.
  • Lubricating oil compositions are used for the smooth operation of internal combustion engines, power transmission components including automatic transmissions, shock absorbers and power steering devices and gears.
  • the engine oils for internal combustion engines in particular serve to (i) lubricate various sliding interfaces eg between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters, (ii) cool the engine, (iii) clean and disperse the combustion products and (iv) prevent corrosion and consequent rust formation.
  • the stringent requirements for high performance engines in recent years has meant greater demand from lubricants used in such engines.
  • Lubricating oils used in such engines usually deteriorate due to oxidation by oxygen and nitrogen oxides (NOx) formed during combustion of fuels and lubricants and that contained in blow-by gas in turn formed by leakage of combustion gases into the crankcase via the piston and cylinder interface.
  • NOx oxygen and nitrogen oxides
  • the concentration of NOx increases in the blow-by gas with increasing demand in performance of the engine.
  • the deleterious effects of oxidation can be and have been mitigated by the use of various additives including antioxidants, anti-wear agents, ash-free detergent dispersants, friction modifiers and the like.
  • the present invention is a lubricating oil composition
  • a base stock and an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula: Mo 3 S x -(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand, and at least one other compound selected from a phenolic and an aminic compound characterised in that the base stock has a kinematic viscosity at 100°C (KNioo) from about 2 cSt to 20 cSt (2 x 10 "6 to 20 x 10 "6 m 2 /sec) and a saturates content of at least 85%.
  • KNioo kinematic viscosity at 100°C
  • the lubricating oil compositions of the present invention are those that comprise a major amount of a Group II or Group III base stock which may be a natural or synthetic lubricating oil having a KNioo of 2-20 cSt, preferably from 2-12 cSt and a saturates content of at least 85%, preferably at least 88%.
  • Specific examples of Group II basestock high in saturates include inter alia RLOP 500R and Mobil Jurong 500 ⁇ (with > 97% saturates), and MXT 5 (with 92% saturates); and examples of Group III basestock include inter alia Yubase 4 (with saturate contents of 99.5%) and Yubase 6 (with saturate contents of 97.5%).
  • the present invention is a method of stabilizing a lubricant composition against oxidative degradation, said composition comprising a base stock which has a kinematic viscosity at 100°C (KNioo) from about 2 cSt to 20 cSt (2 x 10 "6 to 20 x 10 "6 m 2 /sec) and a saturates content of at least 85% said method comprising adding to the basestock an effective amount of an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
  • the trinuclear molybdenum compounds are of formula (I)
  • x is from 4 to 10, preferably 7, and Q is a core group.
  • the core group (Q) may be a ligand capable of rendering the organomolybdenum compound of formula (I) oil soluble and ensuring that said molybdenum compound is substantially charge neutral.
  • the core group (Q) is generally associated with suitable ligands such as L y wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole.
  • suitable ligands such as L y wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole.
  • the trinuclear molybdenum compound used in the compositions of the present invention may be represented by the formula (II):
  • the ligands "L” are suitably dihydrocarbyl dithiocarbamates of the structure (-S CNR 2 ) wherein the dihydrocarbyl groups, R 2 impart oil solubility to the molybdenum compound.
  • hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
  • substituents include the following:
  • hydrocarbon substituents ie, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl), aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group);
  • hetero substituents ie, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
  • the hydrocarbyl groups are preferably alkyl (e.g, in which the carbon atom attached to the remainder of the ligand "L" is primary, secondary or tertiary), aryl, substituted aryl and/or ether groups.
  • the hydrocarbyl groups of the ligands should be such that they have a sufficient number of carbon atoms to render the compound (I) soluble or dispersible in the oil to which the trinuclear organomolybdenum compound containing the ligand is added.
  • the total number of carbon atoms present among all of the hydrocarbyl groups of the organomolybdenum compounds' ligands is suitably at least 21, preferably at least 25, more preferably at least 30 and even more preferably at least 35, typically e.g., 21 to 800.
  • the number of carbon atoms in each hydrocarbyl group will generally range from 1 to 100, preferably from 1 to 40 and more preferably from 3 to 20.
  • the antioxidant in the compositions of the present invention suitably also include at least one other compound selected from a phenolic compound and an aminic compound.
  • phenolic compounds hindered phenols are preferred. Examples of such phenolic compounds include ter alia:
  • antioxidants which are preferred as the antioxidants may be represented by the generic formulae (III) - (IN) below in which R l5 R 2 , and R 3 are the same or different alkyl groups from 3-9 carbon atoms and x and y are integers from 1 to 4.
  • Suitable aminic compounds for use in the compositions of the present invention are diaryl amines, aryl naphthyl amines and alkyl derivatives of diaryl amines and the aryl naphthyl amines.
  • Preferred aminic antioxidants are represented by the formulae (VII) and (VIII) wherein each of ⁇ and R 5 is a hydrogen atom or represents the same or different alkyl groups from 1-8 carbon atoms.
  • Monoalkyldiphenyl amines such as eg monooctyldiphenyl amine and monononyl diphenyl amine; dialkyldiphenyl amines such as eg 4,4'-dibutyldiphenyl amine, 4,4'- dipentyldiphenyl amine, 4,4'-dihexyldiphenyl amine, 4,4'-diheptyldiphenyl amine, 4,4'- dioctyldiphenyl amine and 4,4'-dinonyldiphenyl amine; polyalkyldiphenyl amines such as eg tetra-butyldiphenyl amine, tetra-hexyldiphenyl amine, tetra-octyldiphenyl amine and tetra- nonyldiphenyl amine; the naphthylamines such as eg ⁇ -naphthy
  • the antioxidant which comprises the organomolybdenum compound in combination with a phenolic and/or an aminic compound will form a minor component of the total lubricant composition.
  • the organomolybdenum compound typically will comprise about 0.05 to about 5.00 wt % of the total composition, preferably from 0.05 to 2.0 wt%, and more preferably from 0.1 to 0.7 wt%, i.e., the molybdenum metal is suitably present in an amount of from about 25 to 2500 ppm, preferably from about 50 to 1000 ppm, and more preferably from 100 to 700 ppm, and the phenolic and/or aminic compounds about 0.10 to about 3.0 wt % of the total composition.
  • the antioxidant comprises in addition to the organo molybdenum compound, a mixture of the phenols (III)-(VI) above and the diaryl amines (VII)-(VIII) in a weight ratio ranging from about 80: 10: 10 to about 10:30:60 respectively, preferably typically 50:15:35 respectively.
  • the antioxidants may be combined with a carrier liquid in the form of a concentrate.
  • concentration of the combined antioxidants in the concentrate may vary from 1 to 80% by weight, and will preferably be in the range of 5 to 50% by weight.
  • the antioxidant combination of the present invention can be used with any of the conventional dispersants used hitherto in the lubricating compositions.
  • dispersants include mter alia the polyalkylene succinimides, Mannich condensation products of polylalkylphenol-formaldehyde polyamine and boronated derivatives thereof.
  • ashless dispersants such as the ashless succinimides, especially the polyisobutenyl succinimides of a polyamine such as eg tetraethylenepentamine or its homologues, benzylamine ashless dispersants, and ester ashless dispersants.
  • the dispersants are generally used in the compositions of the present invention in an amount ranging from about 2-10% by weight based on the total weight of the lubricant composition, preferably from about 4-8% by weight.
  • a feature of the present invention is that the compositions of the present invention the presence of a trinuclear organo molybdenum compound facilitates the control of deposit formation from engine oils. More specifically, formulations containing eg a contribution of 200- 750 ppm, preferably from 450-550 ppm of Mo metal from the trimer and an additional contribution of from 80-100 ppm from a detergent inhibitor package enables the amount of deposit formed to be significantly reduced.
  • This reduction in deposit formation has been monitored by the so-called TEOST-MHT-2 test which test is similar to the conventionally used TEOST-33 test method except that it is run at a relatively lower temperature and for a longer time. These tests are especially designed to test the formulations for a GF-3 specification.
  • the TEOST-33 test is carried out at temperature cycles which fluctuate from 200-500°C and last for about 2 hours and results in bulk oxidation of the oil (about 100 g).
  • the TEOST-MHT-2 test relates to high temperature engine deposits as measured in tests such as TU3HT and is carried out at about 285°C over 24 hours and is a thin-film test on about 8 g of oil.
  • the TEOST-MHT-2 test measures deposits produced on a heated rod or in the oil itself (filtered residue) and the GF-3 specification is envisioned to specify a limit of 40 mg deposit. From the results in the Examples below it will be seen that the presence of a trinuclear organo molybdenum compound in such oils results in about 66% reduction in the total weight of the deposits formed which satisfies the GF-3 specification.
  • these lubricating compositions may include additives commonly used in lubricating oils especially crankcase lubricants, such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
  • crankcase lubricants such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
  • a feature of the present invention is that lubricant compositions comprising high saturates base oils and trinuclear organomolybdenum compounds in combination with a phenolic and/or an aminic compound as antioxidant provide unexpected improvement in oxidation control and significant benefits in fuel economy.
  • the present invention confers the added benefits of viscosity increase control and dispersancy retention over compositions which contain only one of these antioxidants used alone.
  • Test oils were prepared. These oils were then tested in a bench oxidation test which was conducted at 165°C under a mixed nitrogen/air flow, with 40 ppm iron from added ferric acetylacetonate as catalyst. The flow rates of air and nitrogen were controlled at 500 ml/min and 350ml/min respectively.
  • Irganox® L57 is an octylated/butylated diphenylamine (ex Ciba Geigy)
  • Irganox® LI 01 is a high molecular weight phenolic antioxidant (ex Ciba Geigy)
  • Irganox® LI 15 and Irganox® L 1035 are high molecular weight phenolic antioxidants with a thioether group (ex Ciba Geigy)
  • Irganox® L06 is an alkylated phenyl- ⁇ -naphthylamine (ex Ciba Geigy)
  • Irganox® LI 35 is a high molecular weight phenolic antioxidant (ex Ciba Geigy)
  • Irganox® LI 50 is a mixture of alkylated diphenylamine, a phenolic antioxidant and a phenolic antioxidant with a thioether group (ex Ciba Geigy)
  • Paranox® 106 is a polyisobutenylsuccinimide dispersant (ex Infenium, Linden, NJ)
  • Molyvan® 822 is a dinuclear molybdenum dithiocarbamate containing 5 % wt molybdenum (ex R T Vanderbilt Co)
  • PDN5203 is an experimental sample of trinucler molybdenum dithiocarbamate containing 5% wt molybdenum
  • Paratone 8451 is a viscosity index improver (ex Oronite)
  • Paraflow®390 is a pour point depressant (ex Oronite)
  • DI is a conventional detergent inhibitor package which is free of a friction modifier package
  • compositions of the test oils in these used in these Examples and their changes m respective viscosities after a 48 hour oxidation test are given m Table 1 below
  • compositions of the test oils in Examples J-Q and their respective changes in viscosity data after a 48-hour oxidation test on each are shown in Table 2 below TABLE 2
  • Examples J-Q show that the trinuclear molybdnum dithiocarbamate gives better performance than conventional dinuclear molybdenum dithiocarbamate in oxidation control.
  • the performance of the trinuclear molybdenum compound is further enhanced in base oils high in saturates.
  • Examples R-U demonstrate that mixtures of aminic and phenolic antioxidants give equivalent performance to an aminic antioxidant.
  • Base oils high in saturates provide additional benefit in viscosity control.
  • Fuel economy is measured in different types of engine tests including the Sequence VIA, Sequence VIB and the Ml 11 tests. Sequence VIA and the Ml 11 tests evaluate initial fuel economy while Sequence VIB test determines initial and retained fuel economy after 96 hours.
  • a 5W-20 formulation comprising a Group II base oil is shown in Table 4 below:
  • the fuel economy and fuel economy retention data were collected using a gasoline passenger car Ml 11 fuel economy test (CES-L54-X-94) and a Ml 11 fuel economy retention test.
  • Ml 11 fuel economy retention test the duration of the test is extended by repeating the standard test cycles 21 times. Each test cycle is followed by a period of steady state aging. The aging is equivalent to 500 miles. The total test is thus equivalent to about 10,000 miles, and takes about 185 hours. Fuel consumptions are measured at every cycle, hence every 500 miles. The fuel consumption reference RL191 is measured both at the beginning and end of the test, thereby allowing uninterrupted aging of the test oil.
  • Example V shows that addition of molybdenum compounds leads to better fuel economy retention in a European gasoline passenger car engine.
  • the use of trinuclear molybdenum dithiocarbamate provides significant improvement in initial fuel economy and fuel economy retention over the conventional dinuclear molybdenum dithiocarbamate.
  • a 5W-20 engine oil formulation comprising a Group III base oil is shown in Table 6 below:
  • Example W further demonstrates the benefit of trinuclear molybdenum dithiocarbamate in fuel economy improvement in a North American gasoline engine.
  • the TEOST-MHT-2 test was performed in a manner very similar to the conventional TEOST-33 test for a GF-2 specification by running at a lower temperature (285°C) but for a longer period of time ie 24 hours on an 8 g sample of oil.
  • the test is set to measure deposits produced on a heated rod or in the oil itself (filtered residue) and it was expected to match the currently given GF-3 specification limit of 40 mg of deposit.
  • Table 8 The results are tabulated in Table 8 below:

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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)
EP01918980A 2000-02-14 2001-02-08 Antioxidantzusatzstoffzusammensetzung für schmieröle Withdrawn EP1280873A1 (de)

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US6642191B2 (en) * 2001-11-29 2003-11-04 Chevron Oronite Company Llc Lubricating oil additive system particularly useful for natural gas fueled engines
US20040142827A1 (en) * 2001-11-29 2004-07-22 Palazzotto John D. Sulfur containing lubricating oil additive system particularly useful for natural gas fueled engines
US6852679B2 (en) 2002-02-20 2005-02-08 Infineum International Ltd. Lubricating oil composition
US7134427B2 (en) 2003-05-22 2006-11-14 Afton Chemical Intangibles Llc Delivery of organomolybdenum via vapor phase from a lubricant source into a fuel combustion system
US20050043191A1 (en) * 2003-08-22 2005-02-24 Farng L. Oscar High performance non-zinc, zero phosphorus engine oils for internal combustion engines
US7494960B2 (en) * 2004-02-03 2009-02-24 Crompton Corporation Lubricant compositions comprising an antioxidant blend
EP2123739B1 (de) * 2008-05-20 2017-09-27 Infineum International Limited Schmierung für einen Schiffsmotor
EP2123740B1 (de) 2008-05-20 2017-08-23 Infineum International Limited Schmierung für einen Schiffsmotor
EP2135926A1 (de) 2008-05-20 2009-12-23 Infineum International Limited Schmierung für einen Schiffsmotor
CN102365352A (zh) * 2009-04-07 2012-02-29 英菲诺姆国际有限公司 船用发动机润滑

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US6010987A (en) * 1996-12-13 2000-01-04 Exxon Research And Engineering Co. Enhancement of frictional retention properties in a lubricating composition containing a molybdenum sulfide additive in low concentration
US5837657A (en) * 1997-12-02 1998-11-17 Fang; Howard L. Method for reducing viscosity increase in sooted diesel oils
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BR0108330A (pt) 2003-03-11
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