WO2010122070A1 - Composition lubrifiante - Google Patents

Composition lubrifiante Download PDF

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Publication number
WO2010122070A1
WO2010122070A1 PCT/EP2010/055294 EP2010055294W WO2010122070A1 WO 2010122070 A1 WO2010122070 A1 WO 2010122070A1 EP 2010055294 W EP2010055294 W EP 2010055294W WO 2010122070 A1 WO2010122070 A1 WO 2010122070A1
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WO
WIPO (PCT)
Prior art keywords
molybdenum
lubricating composition
groups
alkyl groups
zinc dialkyldithiophosphate
Prior art date
Application number
PCT/EP2010/055294
Other languages
English (en)
Inventor
Hideaki Mitsui
Eiji Nagatomi
Tetsuo Wakizono
Mariko Yokoyama
Original Assignee
Shell Internationale Research Maatschappij B.V.
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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2010122070A1 publication Critical patent/WO2010122070A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • 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
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • This invention relates to a lubricating composition which reduces the friction arising at lubrication points in, for example, bearings, gears, engines and gearboxes and which also inhibits wear.
  • lubricating compositions with superior friction and wear characteristics for bearings and gears in the machines and apparatus used in the automobile, steel, rail and other industries. They are particularly important in lubrication applications such as car engines, gearboxes, constant velocity joints in cars where there is a mixture of rolling and sliding friction, and the ball screws used in the driving apparatus of injection moulding machines and electrically powered presses. Wear resistance is also an important characteristic in engine oils.
  • engine oils can be made to give low fuel consumption by combining with organic molybdenum compounds, within certain ranges, imide compounds comprised of polybutenyl succinimides and boron adducts of polybutenyl succinimides, alkaline earth metal sulphonates and alkaline earth metal salicylates. See Japanese Laid-open Patent 2000-34491.
  • Organic molybdenum compounds are used as friction modifiers and their effect in reducing friction is superior to the ashless type of friction modifiers, especially in boundary lubrication domains. They are used not only in engine oils but are added also to lubricating oils for drive systems and industrial machinery. Organic molybdenum compounds are soluble in oil and so do not precipitate out, but it is believed they may decompose on the friction surfaces and form a so-called molybdenum disulphide film on the surfaces of the metals. It is evident that, when they do, this gives rise to interactions with the other additives co-present in the oil.
  • This invention uses an organic molybdenum compound and zinc dialkyldithiophosphate in combination and together with a base oil, but the point is that the alkyl groups of the zinc dialkyldithiophosphate include secondary alkyl groups and primary alkyl groups.
  • the aforementioned organic molybdenum compound is present in an amount not less than 300 ppm in terms of molybdenum, and the ratio of the secondary alkyl and primary alkyl groups of the zinc dithiophosphate alkyl groups is made to be 60 : 40 to 10 : 90.
  • Group I base oils include, for example, paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as solvent refining, hydrorefining, and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Group II base oils include, for example, paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as hydrorefining and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of not more than 5% and so are suitable for use in this invention.
  • Group III base oils and Group 11+ base oils include paraffinic mineral oils manufactured by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by the Isodewax process which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins, and base oils refined by the Mobil wax isomerisation process. These too are suitable for use in this invention.
  • synthetic oils include polyolefins, polyoxyalkylene glycols such as polyethylene glycol or polypropylene glycol, esters such as di-2- ethylhexyl sebacate or di-2-ethylhexyl adipate, polyol esters such as trimethylolpropane esters or pentaerythritol esters, perfluoroalkyl ethers, silicone oils, polyphenyl ethers, and so on.
  • polyolefins polyoxyalkylene glycols such as polyethylene glycol or polypropylene glycol
  • esters such as di-2- ethylhexyl sebacate or di-2-ethylhexyl adipate
  • polyol esters such as trimethylolpropane esters or pentaerythritol esters
  • perfluoroalkyl ethers silicone oils
  • polyphenyl ethers and so on.
  • the aforementioned polyolefins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and ⁇ -olefins with five or more carbons. In the manufacture of polyolefins, one kind of the aforementioned olefins may be used singly or two or more kinds may be used in combination. Particularly suitable are the polyolefins called poly- ⁇ -olefins (PAO) . These are base oils of Group IV.
  • PAO poly- ⁇ -olefins
  • GTLs gas to liquid oils synthesised by the Fischer-Tropsch method of converting natural gas to liquid fuel have a very low sulphur content and aromatic content compared with mineral oil base oils refined from crude oil and have a very high paraffin constituent ratio, and so have excellent oxidative stability, and because they also have extremely small evaporation losses, they are suitable as base oils for this invention.
  • the various kinds of oil mentioned above may be used as base oils either alone or as mixtures, but the aforementioned instances are mere examples and the invention is not limited by these.
  • the zinc dialkyldithiophosphates used in this invention include zinc dialkyldithiophosphate mixtures comprised of a primary zinc dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate.
  • zinc dialkyldithiophosphates mention may be made of those that can be expressed by the following general formula (1) .
  • R 1 , R 2 , R 3 and R 4 each independently denote a primary alkyl group of 2 to 18 carbons but preferably of 4 to 12 carbons, or a secondary alkyl group of 3 to 18 carbons but preferably of 3 to 10 carbons.
  • R 6 denotes a linear or branched alkyl group of 1 to 17 carbons but preferably of 3 to 11 carbons.
  • R 6 include alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups and heptadecyl groups (the alkyl groups may be linear or branched) .
  • a secondary alkyl group of 3 to 18 carbons in this invention is a group expressed by the following general formula (3 ⁇ .
  • R 7 and R 8 each independently denote linear or branched groups in which the number of carbons is 1 to 16, but preferably 1 to 8, and where the total carbons in R 7 and R 8 is 2 to 17, but preferably 2 to 9.
  • R 7 and E 8 mention may be made, for each, of linear of branched methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups and hexadecyl groups.
  • the secondary alkyl zinc dithiophosphates include, for example, zinc mono- or di-sec- butyldithiophosphate, zinc mono- or di-sec- pentyldithiophosphate and zinc mono- or di-4-methyl ⁇ -2 ⁇ pentyldithiophosphate .
  • the zinc dialkyldithiophosphates in this invention have co-present secondary and primary alkyl groups, and the ratio of the secondary and primary alkyl groups may be set at 60 : 40 to 10 : 90, but more preferably 50 : 50 to 10 : 90.
  • the aforementioned organic molybdenum compound includes molybdenum phosphates, molybdenumTMamine complexes, molybdenum dialkyldithiocarbamates, molybdenum, dialkyldithiophosphates and others, but normally it is suitable to use molybdenum dialkyldithiocarbamates and molybdenum dialkyldithiophosphates .
  • molybdenum dialkyldithiocarbamates mention may be made of molybdenum diethyldithiocarbamate, molybdenum dipropyldithiocarbamate, molybdenum dibutyldithiocarbamate, molybdenum dipentyldithiocarbamate, molybdenum dihexyldithiocarbamate, molybdenum dioctyldithiocarbamate, molybdenum didecyldithiocarbamate, molybdenum didodecyldithiocarbaruate, oxymolybdenum diethyldithiocarbamate, oxymolybdenum dipropyldithio
  • molybdenum dialkyldithiophosphates mention may be made of molybdenum diethyldithiophosphate, molybdenum dipropyldithiophosphate, molybdenum dibutyldithiophosphate, molybdenum dipentyldithiophosphate, molybdenum dihexyldithiophosphate, molybdenum dioctyldithiophosphate, molybdenum didecyldithiophosphate, molybdenum didodecyldithiophosphate, oxymolybdenum diethyldithiophosphate, oxymolybdenum dipropyldithiophosphate, oxymolybdenum
  • this organic molybdenum compound as calculated in terms of molybdenum is blended in the total amount of the lubricating composition.
  • an amount of not less than 900 ppr ⁇ of the aforementioned zinc dialkyldithiophosphate as calculated in terms of phosphorus is similarly blended in the total amount of the lubricating composition.
  • the organic molybdenum compound and zinc dialkyldithiophosphate are both blended into the lubricating composition, and the ratio of the secondary alkyl group and the primary alkyl group in this zinc dialkyldithiophosphate is, as mentioned above, 60 : 40 to 10 : 90. If the proportion of the aforementioned secondary alkyl group exceeds 60 mol%, the friction coefficient cannot be reduced effectively, and if the proportion of the primary alkyl group exceeds 90 mol%, the anti-wear performance will decline, which is often not desirable.
  • Suitable amine-based or phenol-based anti-oxidants or the like include sulphurised olefins or sulphurised oils and fats, extreme-pressure/anti-wear agents such as phosphates or phosphites, metal salts such as sulphonates, salicylates and phenates capable of being used as rust inhibitors, structural stabilisers or detergent-dispersants, viscosity modifiers such as viscosity enhancers like polybutenes and polvmethacrylates, solid lubricants such as molybdenum disulphide or boron nitride, dispersants such as succinimides, metal deactivators, pour point depressants, defoar ⁇ ing agents and other known kinds of additives.
  • suitable amine-based or phenol-based anti-oxidants or the like include sulphurised olefins or sulphurised oils and fats, extreme-pressure/anti-wear agents such as phosphates or phosphi
  • the lubricating compositions were prepared by using the base oils and additives shown below in the constituent proportions (weight %) shown in Table 1, and SRV friction and wear tests were carried out as described below.
  • Zinc dithiophosphate shown in the table as secondary ZnDTP (B) :
  • Oronite OLOA 269R ⁇ trade name was used.
  • DI sub-package a blend of the following components corresponding to a GF-2 level.
  • Lubrizol Lz74 1% (Ca sulphonate) , Lubrizol Lz52; 3,5% (Ca sulphonate),
  • Viscosity index improver VII Oronite Paratone 8941

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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 présente invention porte sur une composition lubrifiante contenant un dialkyldithiophosphate de zinc tel que représenté par la formule (1) suivante et un composé organique de molybdène dans une huile de base, les groupes alkyles du dialkyldithiophosphate de zinc comprenant des groupes alkyles secondaires et des groupes alkyles primaires : dans lesquels R1, R2, R3 et R4 représentent chacun un groupe alkyle primaire de 2 à 18 atomes de carbone ou un groupe alkyle secondaire de 3 à 18 atomes de carbone.
PCT/EP2010/055294 2009-04-22 2010-04-21 Composition lubrifiante WO2010122070A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-104337 2009-04-22
JP2009104337A JP2010254767A (ja) 2009-04-22 2009-04-22 潤滑油組成物

Publications (1)

Publication Number Publication Date
WO2010122070A1 true WO2010122070A1 (fr) 2010-10-28

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WO (1) WO2010122070A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113330099A (zh) * 2018-10-26 2021-08-31 Ｋｙｂ株式会社 缓冲器用润滑油组合物、摩擦调整用添加剂、润滑油添加剂、缓冲器及缓冲器用润滑油的摩擦调整方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6325893B2 (ja) * 2014-05-21 2018-05-16 シェルルブリカンツジャパン株式会社 内燃機関用潤滑油組成物
JP6325894B2 (ja) * 2014-05-21 2018-05-16 シェルルブリカンツジャパン株式会社 内燃機関用潤滑油組成物
US11578287B1 (en) * 2021-12-21 2023-02-14 Afton Chemical Corporation Mixed fleet capable lubricating compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113045A1 (fr) * 1982-11-30 1984-07-11 Honda Motor Co., Ltd. Composition d'huile lubrifiante
WO1995015368A1 (fr) * 1993-11-30 1995-06-08 Exxon Research & Engineering Company Composition d'huile lubrifiante
JP2000034491A (ja) 1998-07-17 2000-02-02 Idemitsu Kosan Co Ltd 内燃機関用潤滑油組成物
US6329328B1 (en) * 1999-04-01 2001-12-11 Tonen General Sekiyu K. K. Lubricant oil composition for internal combustion engines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113045A1 (fr) * 1982-11-30 1984-07-11 Honda Motor Co., Ltd. Composition d'huile lubrifiante
WO1995015368A1 (fr) * 1993-11-30 1995-06-08 Exxon Research & Engineering Company Composition d'huile lubrifiante
JP2000034491A (ja) 1998-07-17 2000-02-02 Idemitsu Kosan Co Ltd 内燃機関用潤滑油組成物
US6329328B1 (en) * 1999-04-01 2001-12-11 Tonen General Sekiyu K. K. Lubricant oil composition for internal combustion engines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DAVID M SHOLD: "Engine Lubricant Using Molybdenum Dithiocarbamate As an Antioxidant Top Treatment in High Sulfur Base Stocks", IP.COM JOURNAL, IP.COM INC., WEST HENRIETTA, NY, US, 14 May 2001 (2001-05-14), XP013000414, ISSN: 1533-0001 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113330099A (zh) * 2018-10-26 2021-08-31 Ｋｙｂ株式会社 缓冲器用润滑油组合物、摩擦调整用添加剂、润滑油添加剂、缓冲器及缓冲器用润滑油的摩擦调整方法

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