WO1992016604A1 - Composition de lubrifiant pour moteurs a combustion interne d'une excellente resistance a la chaleur - Google Patents

Composition de lubrifiant pour moteurs a combustion interne d'une excellente resistance a la chaleur Download PDF

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Publication number
WO1992016604A1
WO1992016604A1 PCT/JP1992/000334 JP9200334W WO9216604A1 WO 1992016604 A1 WO1992016604 A1 WO 1992016604A1 JP 9200334 W JP9200334 W JP 9200334W WO 9216604 A1 WO9216604 A1 WO 9216604A1
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WO
WIPO (PCT)
Prior art keywords
oil
soluble
internal combustion
lubricating oil
alkyl
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.)
Ceased
Application number
PCT/JP1992/000334
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English (en)
Japanese (ja)
Inventor
Shunji Watanabe
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.)
NIPPON COOPER Co
Original Assignee
NIPPON COOPER 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 NIPPON COOPER Co filed Critical NIPPON COOPER Co
Publication of WO1992016604A1 publication Critical patent/WO1992016604A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C10M141/08—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 sulfur-, selenium- or tellurium-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
    • 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
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • 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
    • C10N2040/251—Alcohol-fuelled 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to a lubricating oil composition for an internal combustion engine having excellent heat resistance and low-temperature fluidity.
  • Internal combustion engines such as diesel engines and gasoline engines are operated while supplying lubricating oil to valve trains, cylinder inner surfaces, rotating parts, etc., in order to perform high-speed and smooth operation.
  • lubricating oils adhere to the inner surface of the high-temperature cylinder and perform lubrication between the cylinder and the bis-toning ring, they tend to contain fine particles such as soot generated by fuel combustion, moisture, and the like. Exposure to temperature results in oxidation of the lubricating oil itself. Generally, when an internal combustion engine is operated at a high temperature, sulfur oxides and the like are produced by the sulfur content of the fuel. As a result, the acidity in the lubricating oil increases. The increase in acidity is also caused by deterioration of the lubricating oil itself.
  • a lubricating oil composition for an internal combustion engine having excellent heat resistance comprising carbonized i-base oil and the following additives.
  • At least one of the oil-soluble alkyl sulfide compound and the oil-soluble hindered phenol compound is at least 0.2% by weight.
  • composition of the present invention comprises a combination of an oil-soluble alkyl salicylic acid metal salt having an alkyl group of 30 or less carbon atoms and an alkylphenol sulfide.
  • oil-soluble alkyl salicylic acid metal salt having an alkyl group of 30 or less carbon atoms
  • alkylphenol sulfide an alkylphenol sulfide
  • oil-soluble alkali metal salicylic acid which is a component of the lubricating oil of the present invention, include alkali metal elements such as sodium and potassium, alkaline earth metals such as sodium hydroxide, and alkyl salicylic acid. Normal salt is used. Alkaline earth metals, especially calcium, are preferred c
  • normal salt refers to a salt containing an equivalent amount of a metal element and a ligand, and does not include a so-called “overbased” salt containing an excessive amount of a carbon salt.
  • the number of carbon atoms is preferably 3 to 6 carbon atoms, preferably 6 to 22 carbon atoms, and more preferably 6 to 22 carbon atoms. Those having up to 18 alkyl, alkyl, or alkyl groups are preferred. If the number of carbon atoms in the alkyl group of the alkyl salicylic acid group exceeds 30, the salicylate is solidified, which deteriorates the low-temperature fluidity of the lubricating oil composition.
  • Oil-soluble ruquilsalicyl normal salt is, for example, In the method described in Japanese Patent Application Publication No. 600, the metal alkylphenol can be used in an equivalent amount.
  • Oil-soluble ⁇ upper limit of the addition concentration of Rukirusarichiru acid metal normal salt particularly limited, such Iga, 2 4 X 1 0 as the metal component -. If 2 moles / ⁇ or less, is preferable to al.
  • the oil-soluble alkyl sulfide compound is obtained by reacting an alkyl phenol having at least one alkyl-substituted aryl group or aralkyl group having 6 to 24 carbon atoms with sulfur, sulfur chloride or sulfur dichloride to form an alkyl phenol. About 2 to 20 are polymerized.
  • Hindered sulfur phenol compounds are obtained by polymerizing phenols having 10 ortho groups substituted by alkyl or alkoxy having 1 to 8 carbon atoms with sulfur, sulfur chloride or sulfur dichloride in the same manner as described above. It is a thing.
  • Either one or both of the sulfurized tin phenol compound and the alkyl sulfide compound are added in an amount of at least 0.2% by weight.
  • the concentration of the sulfurized hindered phenol compound or the like is less than 0.2% by weight, the thermal stability is undesirably reduced. There is no particular upper limit on the concentration of these compounds, but it is preferably 5% by weight, particularly preferably 3% by weight or less.
  • hydrocarbon base oil any of mineral oil and synthetic oil such as polyalphaolefin may be used.
  • the lubricating oil composition of the present invention may contain, if necessary, various additives such as an oil-soluble ashless dispersant, a friction reducing agent, an antiwear agent, a defoaming agent, and a viscosity index improver in addition to the above-mentioned additives. It may be contained.
  • the oil-soluble ashless dispersant is not particularly limited, but is a mono- or dicarboxylic acid derivative substituted with a polymer of an olefin having 2 to 10 carbon atoms (number average molecular weight, about 700 to 500).
  • a polymer of an olefin having 2 to 10 carbon atoms number average molecular weight, about 700 to 500.
  • derivatives such as polyimide, imido, and ester of polysidenyl succinic acid, or borides thereof are used.
  • the concentration of the oil-soluble ashless dispersant added is usually 0.5% by weight or more.
  • a metal salt of alkyldithiophosphoric acid for example, a zinc salt is used.
  • the addition concentration is usually 0.1 to 2% by weight.
  • Lubricating oil compositions were prepared using the additive compositions shown in Table 1 below and using 500 N (mineral oil) as a base oil, respectively, and these were designated as Specific Example 1 and Comparative Examples 1-4.
  • Comparative Example 1 is a composition containing neither the overbased compound nor the oil-soluble metal alkylsalicylate.
  • the test was carried out by holding the sample at 29 for 16 hours, and the evaluation was made by measuring the increase in viscosity of the sample after the test and the infrared absorbance at 125 cm- 1 . An increase in these measurements indicates that the sample deteriorated.
  • Lubricating oil compositions were prepared using the additive compositions shown in Table 2 below and 150 N (mineral oil) as the base oil, respectively, and used as Specific Examples 2 to 6 and Comparative Example 5.
  • TBN total base number
  • the panel coking test was performed under the condition of 300: 3 hours.
  • the sample for the panel caulking test the sample after the oil strong acid value test using IS ⁇ T was used.
  • lubricating oil compositions were prepared using 500 N (mineral oil) as the base oil. ⁇ 8.
  • the gas oil used in the test had a low sulfur content (0.05% by weight).
  • Materials used were JASOM 3 3 6 — 90 It has the properties described.
  • Each lubricating oil composition was subjected to the first ring groove carbon clogging (volume%), the piston underside clogging, according to the method for testing the cleanliness of automotive diesel engine lubricating oil (JASOM 336-90). Top ring wear (mg) was also tested.
  • Table 4 shows the properties of the lubricating oil composition and the test results.
  • the number of carbon atoms in the alkyl group is a mixture of C 16 to C 18
  • the lubricating oil composition of the present invention has a low level of clogging of the first ring groove carbon, clogging of the piston underside, and topping wear, and has excellent clean dispersibility. I understand.
  • the lubricating oil composition of the present invention di one diesel engine, the heat resistance as an internal combustion machine ⁇ such petrol Rine engine, excellent in low temperature fluidity, useful der c -

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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

Une composition de lubrifiant utilisée dans des moteurs à combustion interne tels que des moteurs diesel et à essence, excellente du point de vue de la résistance à la chaleur et de la fluidité à basse température, comprend une huile d'hydrocarbure utilisée comme huile de base à laquelle on ajoute un sel de métal normal soluble dans l'huile d'un acide alkylesalicylique (comprenant un alkyle C30 ou inférieur) en une quantité d'au moins 2,2x10-3 mol/l en ce qui concerne la teneur en métal, et au moins soit un composé d'alkylephénol sulfurisé soluble dans l'huile soit un composé de phénol entravé sulfurisé soluble dans l'huile en une quantité d'au moins 0,2 % en poids.
PCT/JP1992/000334 1991-03-20 1992-03-19 Composition de lubrifiant pour moteurs a combustion interne d'une excellente resistance a la chaleur Ceased WO1992016604A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5703291 1991-03-20
JP3/57032 1991-03-20

Publications (1)

Publication Number Publication Date
WO1992016604A1 true WO1992016604A1 (fr) 1992-10-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1992/000334 Ceased WO1992016604A1 (fr) 1991-03-20 1992-03-19 Composition de lubrifiant pour moteurs a combustion interne d'une excellente resistance a la chaleur

Country Status (1)

Country Link
WO (1) WO1992016604A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4862804A (fr) * 1971-11-23 1973-09-01
JPS60147497A (ja) * 1984-01-09 1985-08-03 Cosmo Co Ltd サリチレ−トを含有する塩基性硫化アルカリ土類金属フエネ−ト型清浄剤の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4862804A (fr) * 1971-11-23 1973-09-01
JPS60147497A (ja) * 1984-01-09 1985-08-03 Cosmo Co Ltd サリチレ−トを含有する塩基性硫化アルカリ土類金属フエネ−ト型清浄剤の製造方法

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