EP0707623B1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
EP0707623B1
EP0707623B1 EP94918148A EP94918148A EP0707623B1 EP 0707623 B1 EP0707623 B1 EP 0707623B1 EP 94918148 A EP94918148 A EP 94918148A EP 94918148 A EP94918148 A EP 94918148A EP 0707623 B1 EP0707623 B1 EP 0707623B1
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EP
European Patent Office
Prior art keywords
carbon atoms
hydrocarbyl group
composition
oil composition
weight
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.)
Expired - Lifetime
Application number
EP94918148A
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German (de)
English (en)
Other versions
EP0707623A4 (fr
EP0707623A1 (fr
Inventor
Katsuya Arai
Satoshi Asano
Sadao Wada
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ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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Publication of EP0707623A4 publication Critical patent/EP0707623A4/fr
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    • 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
    • C10M163/00—Lubricating 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
    • C—CHEMISTRY; METALLURGY
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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    • C10M137/04—Phosphate esters
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    • 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
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    • C10M159/12—Reaction products
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    • 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
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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    • C10M2223/04—Phosphate esters
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    • 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
    • C10M2223/041—Triaryl phosphates
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    • 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
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    • C10M2223/042—Metal salts thereof
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    • 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
    • C10M2223/049—Phosphite
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/10—Phosphatides, e.g. lecithin, cephalin
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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    • 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
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
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    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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    • 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
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the present invention relates to a lubricating oil composition, in particular, a lubricating oil composition having improved friction reducing properties and suitable for use as a lubricating oil for internal combustion engines, automatic transmissions, suspensions and power steering wheels, particularly as a lubricating oil for internal combustion engines.
  • Lubricating oils are usually used for smoothing the working of internal combustion engines, driving mechanisms such as automatic transmissions, suspensions and power stearings, and gears. Particularly, engine oils are effective in lubricating mainly sliding parts such as a piston ring and a cylinder liner, bearings of a crank shaft or a connecting rod, and valve train including cams and valve lifters; in cooling the engine; in cleaning and dispersing combustion products; and in preventing rust formation and corrosion.
  • additives such as an antiwear agent, metallic detergent, ashless dispersant and antioxidant are incorporated into the engine oil in order to satisfy such requirements.
  • the lubricating oil is used in combination with additives such as a friction modifier (FM) in order to minimize the friction loss and improve the fuel consumption (see, for example, Japanese Patent Publication No. 23595/1991). Further, since the engine oil for automobiles is used under the various conditions of oil temperature, engine speed and load, more excellent frictional properties under the wide-range conditions of use are necessitated for further improving the fuel consumption.
  • FM friction modifier
  • the present invention has been completed after investigations made for the purpose of providing a lubricating oil composition having improved friction reducing properties over those of an ordinary lubricating oil containing molybdenum dithiocarbamate and a phosphoric ester, and is suitable for use as a lubricating oil for internal combustion engines, automatic transmissions, suspensions and power steering wheels, particularly as a lubricating oil for internal combustion engines.
  • the present invention provides a lubricating oil composition which comprises a base oil containing
  • the base oil usable as the major component in the lubricating oil composition of the present invention is not particularly limited.
  • Base oils are those usually used in ordinary lubricating oils, such as mineral oils and synthetic oils.
  • the mineral oils include, for example, 60 neutral oil, 100 neutral oil, 150 neutral oil, 300 neutral oil and 500 neutral oil obtained by solvent refining or hydrorefining; and low-pour point base oils prepared by removing a wax from these base oils so as to improve the low-temperature fluidity. They may be used either singly or in the form of a mixture of two or more of them in a proper ratio.
  • the synthetic oils include, for example, poly-a olefin oligomers, diesters, polyol esters and polyglycol esters. They are usable either singly or in the form of a mixture. They are also usable in the form of a mixture with the above-described mineral oil.
  • the blending weight ratio of the synthetic oil to the mineral oil is, for example, 80:20 to 20:80.
  • a suitable base oil usable in the composition of the present invention is one having a viscosity in the range of 3 to 20 cSt at 100°C. Particularly preferred are hydrocracked products and/or wax isomerized products containing 3.0% by weight or below of an aromatic component and having a sulfur content of 50 ppm or below and a nitrogen content of 50 ppm below.
  • the component (A) is at least one compound selected from the group consisting of a (a) phosphoric ester of the general formula: wherein R 1 , R 2 and R 3 are each as defined above, and (b) phosphorous esters of the general formula: wherein R 4 , R 5 and R 6 are each as defined above.
  • the groups R 1 , R 2 and R 3 in the above general formula [1] may be the same or different and each represents a hydrogen atom or a hydrocarbyl group having 3 to 23 carbon atoms, with the proviso that at least one of R 1 to R 3 is the hydrocarbyl group having 3 to 23 carbon atoms.
  • the hydrocarbyl groups having 3 to 23 carbon atoms include linear, branched and cyclic alkyl and alkenyl groups having 3 to 23 carbon atoms, aryl groups having 6 to 23 carbon atoms, alkylaryl groups having 7 to 23 carbon atoms and arylalkyl groups having 7 to 23 carbon atoms.
  • Examples include propyl, butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl, eicosyl, phenyl, xylyl, benzyl and phenethyl groups.
  • the groups R 4 , R 5 and R 6 in the above general formula [2] for the phosphorous esters may be the same or different and each represents a hydrogen atom or a hydrocarbyl group having 3 to 23 carbon atoms, with the proviso that at least one of R 4 to R 6 is a hydrocarbyl group having 3 to 23 carbon atoms. Examples include those mentioned above with reference to R 1 , R 2 and R 3 in the above general formula [1].
  • composition of the present invention may contain phosphoric esters either singly or in combination of two or more of them and/or the phosphorous esters either singly or in combination of two or more of them as the component (A). Further, a combination of one or more of the phosphoric esters with one or more of the phosphorous esters may be also used.
  • the composition of the present invention must contain the phosphoric ester and/or phosphorus ester as the component (A) in an amount of 0.01 to 0.8% by weight, preferably 0.05 to 0.5% by weight, based on the whole composition.
  • amount of (A) is below 0.01% by weight, no sufficiently low frictional properties can be obtained and, when it exceeds 0.8% by weight, there is no significant further improvement in frictional properties.
  • MoDTC sulfurized oxymolybdenum dithiocarbamates
  • the groups R 7 and R 8 in the above general formula [3] each represent a hydrocarbyl group having 8 to 18 carbon atoms.
  • the hydrocarbyl groups having 8 to 18 carbon atoms include linear and branched alkyl and alkenyl groups having 8 to 18 carbon atoms, and cycloalkyl, aryl, alkylaryl and arylalkyl groups having 8 to 18 carbon atoms. Examples include 2-ethylhexyl, n-octyl, nonyl, decyl, lauryl, tridecyl, palmityl, stearyl, oleyl, eicosyl, butylphenyl and nonylphenyl groups.
  • R 7 and Ry may be the same or different from each other.
  • m and n are positive integers such that the sum of m + n is 4.
  • the MoDTC used as component (B) may be used singly or as a combination of two or more of them.
  • the amount of MoDTC is in the range of 50 to 2,000 ppm, preferably 100 to 1,000 ppm (in terms of molybdenum) based on the whole composition. When the amount of molybdenum is below 50 ppm, no sufficient friction reduction properties can be obtained and when it is above 2,000 ppm, there is no further significant improvement in the frictional properties.
  • a calcium salicylate having a total base number of 10 to 100 is used as the component (C) in the composition of the present invention.
  • the calcium salicylate is, for example, one represented by the following general formula:
  • the group R 9 in the general formula [4] represents a linear, branched or cyclic alkyl group having 8 to 23 carbon atoms, such as an octyl, nonyl, decyl, dodecyl, pentadecyl, octadecyl or eicosyl group.
  • the calcium salicylate used as component (C) may be used either singly or in combination of two or more of them.
  • the amount of the calcium salicylate is in the range of 0.3 to 2.5% by weight based on the whole composition. When the amount of (C) is below 0.3% by weight, no sufficient low frictional properties can be obtained and, when the amount exceeds 2.5% by weight, the wear resistance is reduced and the ash content is increased unfavorably.
  • the lubricating oil composition of the present invention may contain suitable additives usually incorporated into lubricating oils, such as an ashless detergent-dispersant, viscosity index improver, pour point depressant, antioxidant, rust inhibitor, corrosion inhibitor, antifoaming agent and other antiwear agent and friction modifier, so far as the object of the present invention is not disturbed.
  • suitable additives usually incorporated into lubricating oils, such as an ashless detergent-dispersant, viscosity index improver, pour point depressant, antioxidant, rust inhibitor, corrosion inhibitor, antifoaming agent and other antiwear agent and friction modifier, so far as the object of the present invention is not disturbed.
  • the ashless detergent-dispersants include, for example, succinimides, succinamides, benzylamines, their boron derivatives and esters. They are used in an amount of usually 0.5 to 7% by weight, based on the whole composition.
  • the viscosity index improvers include, for example, polymethacrylates, polyisobutylenes, ethylene/propylene copolymers and hydrogenated styrene/butadiene copolymers. They are used in an amount of from 0.5 to 35% by weight, based on the whole composition.
  • the anti-oxidants include, for example, amine antioxidants such as alkylated diphenylamines, phenyl-a-naphthylamines and alkylated ⁇ -naphthylamines, and phenolic antioxidants such as 2,6-di-t-butyl-4-methyl-phenol and 4,4'-methylenebis(2,6-di-t-butyl-4-methyl-phenol and 4,4'-methylenebis(2,6-di-t-butylphenyl). They are used in an amount of usually 0.05 to 2% by weight, based on the whole composition.
  • amine antioxidants such as alkylated diphenylamines, phenyl-a-naphthylamines and alkylated ⁇ -naphthylamines
  • phenolic antioxidants such as 2,6-di-t-butyl-4-methyl-phenol and 4,4'-methylenebis(2,6-di-t-butyl
  • the rust inhibitors include, for example, alkenylsuccinic acids and partial esters thereof.
  • the corrosion inhibitors include, for example, benzotriazole and benzimidazole.
  • the antifoaming agents include, for example, dimethylpolysiloxanes and polyacrylates. They can be suitably incorporated into the oil composition.
  • the coefficient of friction of the lubricating oil composition was determined as follows:
  • the coefficient of friction was determined by the LFW-1 test under the conditions of 270 rpm, 30 kgf, 120°C and 10 minutes.
  • Base oil 150N-1 (having viscosity at 100°C of 5.7 mm 2 /s, aromatic component content of 4.1 wt%, sulfur content of 11.0 ppm and nitrogen content of 89.0 ppm) or 150N-2 (having viscosity at 100°C of 5.5 mm 2 /s, aromatic component content of 0.5 wt%, sulfur content of 0.5 ppm and nitrogen content of 0.1 ppm) was used.
  • a lubricating oil containing the combination of salicylate, MoDTC and phosphoric ester according to the invention provides a significantly lower coefficient of friction over an oil composition containing any two components.
  • the lubricating oil composition of the present invention has superior low frictional properties to those of ordinary lubricating oils comprising MoDTC and a phosphoric ester, and is suitable for use as a lubricating oil for, for example, internal combustion engines, automatic transmissions, suspensions and power steering wheels, particularly as a lubricating oil for internal combustion engines.

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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

Composition d'huile lubrifiante contenant de 0,01 à 0,8 % en poids, par rapport à la composition totale, d'un ester phosphorique et/ou d'un ester phosphoreux, de 50 à 2000 ppm (exprimées en molybdène) de dithiocarbamate d'oxymolybdène sulfuré comprenant au moins un groupe hydrocarbyle contenant 8 à 18 atomes de carbone, et de 0,3 à 2,5 % en poids d'un salicylate de calcium présentant une basicité totale comprise entre 10 et 100.

Claims (5)

  1. Composition d'huile lubrifiante qui comprend une huile de base contenant:
    (A) 0,01 à 0,8% en poids, par rapport à la composition totale, d'au moins un composé sélectionné dans le groupe constitué
    (a) d'esters phosphoriques de formule générale :
    Figure 00160001
    dans laquelle R1, R2 et R3 peuvent être identiques ou différents et représentent chacun un atome d'hydrogène ou un groupe hydrocarbyle ayant 3 à 23 atomes de carbone, à condition qu'au moins l'un des groupes R1 à R3 soit un groupe hydrocarbyle ayant 3 à 23 atomes de carbone, et
    (b) d'esters phosphoreux de formule générale :
    Figure 00160002
    dans laquelle R4, R5 et R6 peuvent être identiques ou différents et représentent chacun un atome d'hydrogène ou un groupe hydrocarbyle ayant 3 à 23 atomes de carbone, à condition qu'au moins l'un des groupes R4 à R6 soit un groupe hydrocarbyle ayant 3 à 23 atomes de carbone,
    (B) 50 à 2000 ppm, en terme de molybdène, sur la base de la composition totale, de dithiocarbamate d'oxymolybdène sulfurisé ayant au moins un groupe hydrocarbyle ayant 8 à 18 atomes de carbone, et
    (C) 0,3 à 2,5% en poids, par rapport à la composition totale, d'un salicylate de calcium ayant un indice de base total de 10 à 100.
  2. Composition d'huile selon la revendication 1, dans laquelle l'huile de base est un produit hydrocraqué et/ou un produit isomérisé à base de cire contenant 3,0% en poids, par rapport à l'huile de base, ou moins, d'un composant aromatique et ayant une teneur en soufre de 50 ppm ou moins et une teneur en azote de 50 ppm ou moins.
  3. Composition d'huile selon la revendication 1 ou 2, dans laquelle la quantité de composant (A) est de 0,05 à 0,5% en poids par rapport à la composition totale.
  4. Composition d'huile selon l'une quelconque des revendications précédentes, dans laquelle le dithiocarbamate d'oxymolybdène sulfurisé a pour formule :
    Figure 00170001
    dans laquelle R7 et R8 sont chacun indépendamment un groupe hydrocarbyle ayant 8 à 18 atomes de carbone et la somme (m + n) est égale à 4.
  5. Composition d'huile selon l'une quelconque des revendications précédentes, dans laquelle le salicylate de calcium a pour formule :
    Figure 00170002
    dans laquelle R9 est un groupe alkyle linéaire, ramifié ou cyclique ayant 8 à 23 atomes de carbone.
EP94918148A 1993-05-27 1994-05-27 Composition d'huile lubrifiante Expired - Lifetime EP0707623B1 (fr)

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NO954708D0 (no) 1995-11-21
DE69411922D1 (de) 1998-08-27
WO1994028094A1 (fr) 1994-12-08
NO954708L (no) 1995-11-21
CA2163207C (fr) 2002-11-26
DE69411922T2 (de) 1998-12-17
AU6959494A (en) 1994-12-20
NO312680B1 (no) 2002-06-17
EP0707623A4 (fr) 1996-09-18
AU696014B2 (en) 1998-08-27
EP0707623A1 (fr) 1996-04-24
CA2163207A1 (fr) 1994-12-08
JPH06336593A (ja) 1994-12-06

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