WO2014157383A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2014157383A1
WO2014157383A1 PCT/JP2014/058632 JP2014058632W WO2014157383A1 WO 2014157383 A1 WO2014157383 A1 WO 2014157383A1 JP 2014058632 W JP2014058632 W JP 2014058632W WO 2014157383 A1 WO2014157383 A1 WO 2014157383A1
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Prior art keywords
base oil
meth
viscosity
oil
poly
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PCT/JP2014/058632
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English (en)
Japanese (ja)
Inventor
一生 田川
和章 早坂
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Ｊｘ日鉱日石エネルギー株式会社
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Application filed by Ｊｘ日鉱日石エネルギー株式会社 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Priority to US14/779,171 priority Critical patent/US20160053196A1/en
Priority to CN201480030452.2A priority patent/CN105247026B/zh
Publication of WO2014157383A1 publication Critical patent/WO2014157383A1/fr

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    • 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
    • C10M129/68—Esters
    • C10M129/70—Esters of monocarboxylic acids
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • 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
    • C10M169/00—Lubricating 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
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • 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
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention relates to a lubricating oil composition.
  • a method for increasing the viscosity index of the lubricating oil composition there is a method using a lubricating base oil having a high viscosity index such as highly refined mineral oil.
  • a method for producing a high-viscosity index base oil a method of refining a lubricating base oil by hydrocracking / hydroisomerization of a raw material oil containing natural or synthetic normal paraffin is known (for example, patent document). (See 1-3).
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a lubricating oil composition in which both the high viscosity index and the low temperature fluidity are sufficiently enhanced.
  • the present inventor first examined the cause of the difference in the combined effect depending on the combination of the high viscosity index base oil and the pour point depressant.
  • the degree of isomerization ie, the ratio of isoparaffin / normal paraffin
  • the molecular structure of isoparaffin it was found that the effectiveness of the pour point depressant differs depending on the difference (such as the number of carbon atoms from the terminal to the branching position).
  • the present inventor even when using a lubricating base oil containing a large amount of isoparaffin having a large number of carbons from the terminal to the branch position, the lubricating base oil By adding a specific poly (meth) acrylate pour point depressant to the above, it was found that the high viscosity index and the low temperature fluidity can be sufficiently enhanced, and the present invention has been completed.
  • the present invention provides a lubricating base oil having a kinematic viscosity at 100 ° C. of 3.5 to 4.5 mm 2 / s, a viscosity index of 145 or more, and a urea adduct value of 2 to 7% by mass;
  • the proportion of structural units is 0 to 10 mol%, and the proportion of structural units represented by the general formula (1) and R 2 is an alkyl group having 12 or more carbon atoms is 90 to 100 mol%.
  • the average carbon number of the alkyl group having 12 or more carbon atoms in the poly (meth) acrylate pour point depressant is 13 to 16, Provided is a lubricating oil composition wherein the poly (meth) acrylate pour point depressant has a weight average molecular weight of 10,000 to 200,000.
  • the kinematic viscosity and viscosity index at 100 ° C. and the kinematic viscosity at 40 ° C. described later are the viscosity index measured according to JIS K 2283-1993 and the kinematic viscosity at 40 ° C. or 100 ° C., respectively. Means.
  • the urea adduct value as used in the present invention is measured by the following method. 100 g of weighed sample oil (lubricating base oil) is placed in a round bottom flask, 200 g of urea, 360 ml of toluene and 40 ml of methanol are added and stirred at room temperature for 6 hours. As a result, white granular crystals are produced as urea adducts in the reaction solution. The reaction solution is filtered through a 1 micron filter to collect the produced white granular crystals, and the obtained crystals are washed 6 times with 50 ml of toluene.
  • the recovered white crystals are put in a flask, 300 ml of pure water and 300 ml of toluene are added, and the mixture is stirred at 80 ° C. for 1 hour.
  • the aqueous phase is separated and removed with a separatory funnel, and the toluene phase is washed three times with 300 ml of pure water.
  • a desiccant sodium sulfate
  • the ratio (mass percentage) of the urea adduct obtained in this way to the sample oil is defined as the urea adduct value.
  • the weight average molecular weight as used in the field of this invention means the weight average molecular weight (styrene conversion value) by gel permeation chromatograph analysis (GPC).
  • a lubricating oil composition in which both the high viscosity index and the low temperature fluidity are sufficiently enhanced.
  • the lubricating oil composition according to an embodiment of the present invention has a kinematic viscosity at 100 ° C. of 3.5 to 4.5 mm 2 / s, a viscosity index of 145 or more, and a urea adduct value of 2 to 7% by mass.
  • a lubricant base oil The following general formula (1): [In Formula (1), R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group.
  • the structural unit represented by the general formula (1) and R 2 is a methyl group, based on the total amount of the structural unit represented by the general formula (1) contained in the poly (meth) acrylate pour point depressant.
  • the proportion of the structural unit represented by the general formula (1) and R 2 is an alkyl group having 12 or more carbon atoms is 90 to 100 mol%.
  • the alkyl group having 12 or more carbon atoms has an average carbon number of 13 to 16.
  • the poly (meth) acrylate pour point depressant has a weight average molecular weight of 10,000 to 200,000.
  • a kinematic viscosity at 100 ° C. of the lubricating base oil is 3.5 ⁇ 4.5mm 2 / s, preferably 3.6 ⁇ 4.3mm 2 / s.
  • the viscosity index of the lubricating base oil is 145 or more, preferably 147 or more, more preferably 150 or more, from the viewpoint of viscosity-temperature characteristics.
  • the kinematic viscosity at 40 ° C. of the lubricating base oil is not particularly limited, but is preferably 14 to 20 mm 2 / s, more preferably 15 to 19 mm 2 / s.
  • the urea adduct value of the lubricating base oil is 2 to 7% by mass as described above, preferably 3 to 7% by mass, more preferably from the viewpoint of improving the low temperature viscosity characteristic without impairing the viscosity-temperature characteristic. Is 4 to 7% by mass. Further, it is preferable that the urea adduct value is within the above range because the dewaxing condition can be relaxed and the economy is excellent when performing the dewaxing process in the manufacturing process of the lubricating base oil.
  • the manufacturing method of the lubricating base oil is not particularly limited as long as the kinematic viscosity at 100 ° C., the viscosity index, and the urea adduct value can satisfy the above conditions.
  • vacuum distillation distillate (WVGO), WVGO mild hydrocracking (MHC) treated oil (HIX), debris oil (DAO), DAO MHC treated oil or a mixture thereof or a mixture of two or more thereof By suitably hydrocracking oil as a raw material in the presence of a hydrocracking catalyst and further performing a combination of dearomatic treatment and dewaxing treatment, the lubricating base oil according to the present embodiment is suitably obtained. Can do.
  • WVGO is a distillate obtained by distilling residual oil from a crude oil atmospheric distillation apparatus with a vacuum distillation apparatus, and preferably has a boiling point of 360 ° C to 530 ° C.
  • HIX is WHCGO treated with MHC (total pressure is 100 kg / cm 2 or less, preferably 60 to 90 kg / cm 2 , temperature is 370 to 450 ° C., preferably 400 to 430 ° C., LHSV is 0.5 to 4.0 hr. ⁇ 1 , preferably 1.0 to 2.0 hr ⁇ 1 , which means 360 ° C. + a relatively mild hydrogenolysis with a fraction decomposition rate of 20-30 wt%. Heavy vacuum gas oil.
  • a catalyst for the MHC treatment a sulfide obtained by supporting a Group VI metal and a Group VIII metal on a composite oxide carrier such as alumina, silica alumina, and alumina boria can be used.
  • a promoter such as a phosphorus compound may be added to alumina.
  • the amount of the supported metal is 5 to 30 wt%, preferably 10 to 25 wt% for a Group VI metal such as molybdenum, tungsten, and chrome on an oxide basis, and 1 to 10 wt% for a Group VIII metal such as cobalt and nickel, Preferably, it is in the range of 2 to 10 wt%.
  • WVGO and HIX it is preferable to mix 50 wt% or more of HIX with WVGO.
  • the above-mentioned debris oil is an oil that does not contain substantial asphaltenes obtained by distilling residual oil from a crude oil atmospheric distillation apparatus with a vacuum distillation apparatus and treating the residual oil obtained by the propane removal process.
  • the total pressure is 150 kg / cm 2 or less, preferably 100 to 130 kg / cm 2 at medium to low pressure
  • the temperature is 360 to 440 ° C., preferably 370 to 430 ° C.
  • LHSV is low LHSV of 0.5 hr ⁇ 1 or less, preferably 0.2 to 0.3 hr ⁇ 1
  • hydrogen to feedstock ratio is 1,000 to 6,000 s. c. f / bbl-feed oil, preferably 2,500 to 5,000 s. c. f / bbl—can be carried out under reaction conditions that are feedstock.
  • the reaction conditions are adjusted so that the cracking rate of the 360 ° C. + fraction in the feedstock is 40 wt% or more, preferably 45 wt% or more, more preferably 50 wt% or more.
  • the total decomposition rate of the MHC treatment and hydrocracking is 60 wt% or more, preferably 70 wt% or more.
  • the decomposition rate here refers to the decomposition rate per fresh field, not the decomposition rate including the recycled oil.
  • the catalyst used for hydrocracking preferably has a dual function. Specifically, for example, a hydrogenation point composed of a Group VIb metal and a Group VIII iron group metal, a Group III, a Group IV, and the like. And a catalyst having a decomposition point composed of a complex oxide of Group V elements.
  • the Group VIb metal includes tungsten and molybdenum
  • the Group VIII iron group metal includes nickel, cobalt, and iron, and these are finally used as sulfides after being supported on the composite oxide support.
  • the composite oxide used for the carrier includes silica alumina, silica zirconia, silica titania, silica magnesia, silica alumina zirconia, silica alumina titania, silica alumina magnesia, etc., crystalline silica alumina (zeolite), crystalline alumina phosphate (ALPO) ), Crystalline silica aluminate phosphate (SAPO) may be used.
  • the amount of the metal supported on the composite oxide is 5 to 30% by mass, preferably 10 to 25% by mass for the Group VIb metal, and 1 to 20% by mass for the Group VIII iron group metal, preferably based on the oxide. 5 to 15% by mass.
  • a pretreatment catalyst excellent in desulfurization and / or denitrification ability.
  • a sulfide obtained by supporting a Group VI metal and a Group VIII metal on a support such as alumina or alumina boria can be used.
  • a promoter such as a phosphorus compound may be added to alumina or alumina boria.
  • the lubricating oil fraction may be recovered from the cracked product by a normal distillation operation if necessary.
  • Lubricating oil fractions that can be recovered include 70 pail fractions with a boiling range of 343 ° C to 390 ° C, 390 ° C to 445 ° C SAE-10 fraction, 445 ° C to 500 ° C SAE-20 fraction, 500 ° C SAE-30 fraction at 565 ° C.
  • hydrocracked product from which the lubricating oil fraction has been separated and recovered as necessary is dewaxed and then dearomatized, or after dearomatized and dewaxed. Is done.
  • dewaxing treatment solvent dewaxing treatment or contact dewaxing treatment can be adopted.
  • the solvent dewaxing treatment can be performed by a usual method such as MEK method.
  • the MEK method uses benzene, toluene, acetone or a mixed solvent such as benzene, toluene, methyl ethyl ketone (MEK) as a solvent.
  • the processing conditions are such that the cooling temperature is adjusted so that the dewaxed oil reaches a predetermined pour point.
  • the solvent / oil volume ratio is 0.5 to 5.0, preferably 1.0 to 4.5, and the temperature is ⁇ 5 to ⁇ 45 ° C., preferably ⁇ 10 to ⁇ 40 ° C.
  • the contact dewaxing treatment can be performed by a usual method.
  • pentasil-type zeolite is used as a catalyst, and the reaction temperature is adjusted so that the dewaxed oil has a predetermined pour point under hydrogen flow.
  • the reaction conditions are generally 10 to 70 kg / cm 2 , preferably 20 to
  • the temperature is 50 kg / cm 2 and the temperature is 240 to 400 ° C., preferably 260 to 380 ° C.
  • LHSV is in the range of 0.1 to 3.0 hr ⁇ 1 , preferably 0.5 to 2.0 hr ⁇ 1 .
  • solvent dearomatic treatment either solvent dearomatic treatment or high-pressure hydrodearomatic treatment can be adopted, but solvent dearomatic treatment is preferred.
  • the solvent dearomatic treatment usually uses a solvent such as furfural or phenol, but in the present invention, it is preferable to use furfural as the solvent.
  • the solvent dearomatic treatment is carried out at a solvent / oil volume ratio of 4 or less, preferably 3 or less, more preferably 2 or less, at a temperature of 90 to 150 ° C., and the raffinate yield is 60% by volume or more, preferably 70. It is operated so that the volume% or more, more preferably 85 volume% or more.
  • the dearomatic treatment by high-pressure hydrogenation reaction is usually performed in the presence of a catalyst obtained by supporting a group VIb metal and a group VIII iron group metal on an alumina support, and a total pressure of 150 to 200 kg / cm 2 , preferably 70 to 200 kg. / Cm 2 , temperature 280 to 350 ° C., preferably 300 to 330 ° C., LHSV 0.2 to 2.0 hr ⁇ 1 , preferably 0.5 to 1.0 hr ⁇ 1 .
  • the amount of metal supported on the catalyst is 5 to 30% by weight, preferably 10 to 25% by weight of Group VIb metal such as molybdenum, tungsten, and chromium, and Group VIII iron group metal such as cobalt and nickel based on oxide. It is 1 to 10% by mass, preferably 2 to 10% by mass.
  • a hydrogenation treatment can be performed after this treatment as necessary.
  • the solvent-dearomatized oil is treated with a group VIb metal and a group VIII on an alumina support under hydrogenation reaction conditions under a total reaction pressure of 50 kg / cm 2 or less, preferably 25 to 40 kg / cm 2. It is carried out by bringing the iron group metal into contact with a sulfided hydrogenation catalyst.
  • Such a hydrotreatment under a relatively low pressure dramatically improves the light stability of the solvent-dearomatized oil.
  • the amount of the metal supported is 5 to 30% by mass, preferably 10 to 25% by mass of a Group VIb metal such as molybdenum, tungsten, and chromium, preferably 1 to 25% of a Group VIII iron group metal such as cobalt and nickel. It is 10% by mass, preferably 2 to 10% by mass.
  • the lubricating oil fraction when the lubricating oil fraction is not recovered from the hydrocracked product of the raw material oil during the production process, the dearomatic treatment, dewaxing treatment or hydrogen After the chemical conversion treatment, the lubricating oil fraction can be recovered by a normal distillation operation.
  • the lubricating base oil according to the present embodiment other properties are not particularly limited as long as the kinematic viscosity at 100 ° C., the viscosity index, and the urea adduct value satisfy the above conditions, but the lubricating base oil according to the present embodiment is not limited. Preferably satisfies the following conditions.
  • the content of the saturated component in the lubricating base oil according to this embodiment is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more, based on the total amount of the lubricating oil base oil. .
  • the proportion of the cyclic saturated component in the saturated component is preferably 0.1 to 60% by mass, more preferably 0.5 to 55% by mass, still more preferably 1 to 52% by mass, and particularly preferably 5 to 50%. % By mass.
  • the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricating base oil. Furthermore, when the content of the saturated component and the ratio of the cyclic saturated component in the saturated component satisfy the above conditions, the friction characteristics of the lubricating base oil itself can be improved, and as a result, the friction reducing effect is improved. As a result, energy saving can be improved.
  • the content of the saturated component is less than 90% by mass, the viscosity-temperature characteristics, thermal / oxidation stability, and friction characteristics tend to be insufficient. Further, when the ratio of the cyclic saturated component to the saturated component is less than 0.1% by mass, when the additive is blended with the lubricating base oil, the solubility of the additive becomes insufficient, and the lubricating base Since the effective amount of the additive dissolved and retained in the oil is reduced, the function of the additive tends to be unable to be obtained effectively. Furthermore, when the ratio of the cyclic saturated component in the saturated component exceeds 60% by mass, the effectiveness of the additive tends to be reduced when the additive is blended with the lubricating base oil.
  • the ratio of the cyclic saturated component in the saturated component being 30 to 50% by mass is equivalent to the non-cyclic saturated component in the saturated component being 70 to 50% by mass.
  • the non-cyclic saturated component includes both normal paraffin and isoparaffin.
  • the ratio of normal paraffin and isoparaffin in the lubricating base oil according to the present embodiment is not particularly limited as long as the urea adduct value satisfies the above conditions, but the ratio of isoparaffin is preferably 40 to 40 based on the total amount of the lubricating base oil. It is 70% by mass, more preferably 42 to 65% by mass, still more preferably 44 to 60% by mass, and particularly preferably 45 to 55% by mass.
  • content of the saturated part as used in the field of this invention means the value (unit: mass%) measured based on ASTM D 2007-93.
  • the ratio of the cyclic saturated portion and the non-cyclic saturated portion in the saturated portion as used in the present invention means the naphthene portion measured in accordance with ASTM D 2786-91, respectively (measurement object: 1 ring to 6 ring naphthene, unit : Mass%) and alkane content (unit: mass%).
  • the ratio of normal paraffin in the lubricating base oil as used in the present invention means that the saturated fraction separated and fractionated by the method described in ASTM D 2007-93 is subjected to gas chromatography analysis under the following conditions. This means a value obtained by converting the measured value when the ratio of normal paraffin in the saturated content is identified and quantified, based on the total amount of the lubricating base oil.
  • a normal paraffin mixed sample having 5 to 50 carbon atoms is used as a standard sample, and the normal paraffin in the saturates is the total peak area value of the chromatogram (peak derived from the diluent). Is obtained as a ratio of the sum of peak area values corresponding to each normal paraffin.
  • the ratio of isoparaffin in the lubricating base oil means a value obtained by converting the difference between the non-cyclic saturated component in the saturated component and the normal paraffin component in the saturated component, based on the total amount of the lubricant base oil. .
  • a similar method can be used in which a similar result can be obtained in the method of separating saturated components, or in analyzing the composition of cyclic saturated components and non-cyclic saturated components.
  • a method described in ASTM D 2425-93, a method described in ASTM D 2549-91, a method using high performance liquid chromatography (HPLC), a method obtained by improving these methods, and the like can be given.
  • the aromatic content in the lubricating base oil according to the present embodiment is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1% based on the total amount of the lubricating base oil. To 1% by mass, particularly preferably 0.1 to 0.5% by mass. If the aromatic content exceeds the above upper limit, viscosity-temperature characteristics, thermal / oxidation stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to be reduced. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present embodiment may not contain an aromatic component, but the solubility of the additive can be improved by setting the aromatic content to 0.05% by mass or more. It can be further increased.
  • the aromatic content here means a value measured in accordance with ASTM D 2007-93.
  • the aromatic component includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols and naphthols. Aromatic compounds having atoms are included.
  • The% C p of the lubricating base oil according to this embodiment is preferably 80 or more, more preferably 82 to 99, still more preferably 85 to 98, particularly preferably 90 to 97. If% C p value of the lubricating base oil is less than 80, the viscosity - temperature characteristics tend to heat and oxidation stability and frictional properties will be lowered, further, the when the additive is blended into a lubricating base oil The effectiveness of the additive tends to decrease. Further, when the% C p value of the lubricating base oil exceeds 99, the additive solubility will tend to be lower.
  • % C N of the lubricating base oil of the present embodiment is preferably 20 or less, more preferably 15 or less, more preferably 1 to 12, more preferably from 3 to 10. If the% C N value of the lubricating base oil exceeds 20, the viscosity - temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced. Moreover, when% CN is less than 1, the solubility of the additive tends to decrease.
  • % C A of the lubricating base oil of the present embodiment is preferably 0.7 or less, more preferably 0.6 or less, more preferably from 0.1 to 0.5.
  • % C A of the lubricating base oil exceeds 0.7, the viscosity - temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced.
  • % C A of the lubricating base oil of the present embodiment may be 0% by 0.1 or more C A, it is possible to further increase the solubility of additives.
  • the% preferably C P /% C N is 7 or more, more preferably 7.5 or more 8 or more is more preferable.
  • % C P /% C N is less than 7
  • viscosity-temperature characteristics, thermal / oxidative stability and friction characteristics tend to decrease, and further when an additive is blended in the lubricating base oil.
  • the effectiveness of the additive tends to decrease.
  • % C P /% C N is preferably 200 or less, more preferably 100 or less, more preferably 50 or less, particularly preferably 25 or less.
  • % C P ,% C N and% C A are the total carbon number of paraffin carbons determined by a method (ndM ring analysis) based on ASTM D 3238-85, respectively.
  • the iodine value of the lubricating base oil according to the present embodiment is preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.15 or less, and less than 0.01. Although it may be present, it is preferably 0.001 or more, and more preferably 0.05 or more, from the viewpoint of small effects that are commensurate with it and economy.
  • the thermal and oxidation stability can be dramatically improved.
  • the iodine value as used in the field of this invention means the iodine value measured by the indicator titration method of JIS K0070 "acid value, saponification value, iodine value, hydroxyl value, and unsaponification value of a chemical product.”
  • the sulfur content in the lubricating base oil according to the present embodiment depends on the sulfur content of the raw material.
  • the sulfur content is preferably 10 mass ppm or less, from the viewpoint of further improving thermal and oxidation stability and reducing sulfur content, preferably 5 mass ppm or less. More preferably, it is more preferably 3 ppm by mass or less.
  • the content of nitrogen in the lubricating base oil according to this embodiment is not particularly limited, but is preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, and further preferably 1 ppm by mass or less. If the nitrogen content exceeds 5 ppm by mass, the thermal and oxidation stability tends to decrease.
  • the nitrogen content in the present invention means a nitrogen content measured according to JIS K 2609-1990.
  • the pour point of the lubricating base oil according to the present embodiment is preferably ⁇ 7.5 ° C. or less, more preferably ⁇ 10 ° C. or less, and further preferably ⁇ 12.5 ° C. or less.
  • the pour point as used in the present invention means a pour point measured according to JIS K 2269-1987.
  • the CCS viscosity of the lubricating base oil according to the present embodiment at ⁇ 35 ° C. is preferably 2000 mPa ⁇ s or less, more preferably 1800 mPa ⁇ s or less, and further preferably 1700 mPa ⁇ s or less.
  • the CCS viscosity at ⁇ 35 ° C. exceeds the upper limit, the low-temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease.
  • the CCS viscosity at ⁇ 35 ° C. means a viscosity measured according to JIS K 2010-1993.
  • [rho 15 of the lubricating base oil of the present embodiment is preferably 0.85 g / cm 3 or less, more preferably 0.84 g / cm 3 or less.
  • the density at 15 ° C. in the present invention means a density measured at 15 ° C. in accordance with JIS K 2249-1995.
  • the AP of the lubricating base oil according to this embodiment is preferably 110 ° C. or higher, more preferably 115 ° C. or higher.
  • aniline point as used in the field of this invention means the aniline point measured based on JISK2256-1985.
  • the distillation properties of the lubricating base oil according to the present embodiment are preferably such that, by gas chromatography distillation, the initial boiling point (IBP) is 350 to 370 ° C. and the end point (FBP) is 480 to 520 ° C.
  • IBP initial boiling point
  • FBP end point
  • IBP and FBP mean distillate points measured according to ASTM D 2887-97, respectively.
  • the residual metal content in the lubricating base oil according to the present embodiment is derived from the metal content contained in the catalyst and raw materials that are inevitably mixed in the manufacturing process, but such residual metal content may be sufficiently removed.
  • the contents of Al, Mo, and Ni are each preferably 1 mass ppm or less. When the content of these metals exceeds the above upper limit value, the function of the additive added to the lubricating base oil tends to be inhibited.
  • the residual metal content in the present invention means a metal content measured in accordance with JPI-5S-38-2003.
  • the poly (meth) acrylate viscosity index improver includes a structural unit represented by the general formula (1).
  • the structural unit represented by the general formula (1) and R 2 is a methyl group, based on the total amount of the structural unit represented by the general formula (1) contained in the poly (meth) acrylate pour point depressant.
  • the proportion is 0 to 10 mol%, preferably 0 to 5 mol%, particularly preferably 0 mol%. When the ratio exceeds the upper limit, the low temperature viscosity characteristic of the lubricating oil composition becomes insufficient.
  • the alkyl represented by the general formula (1) and R 2 is an alkyl having 12 or more carbon atoms.
  • the proportion of the structural unit as a group is 90 to 100 mol%, preferably 95 to 100 mol%, particularly preferably 100 mol%.
  • the ratio is less than the lower limit, the low temperature viscosity characteristic of the lubricating oil composition becomes insufficient.
  • the alkyl group having 12 or more carbon atoms may be either a linear alkyl group or a branched alkyl group.
  • the average carbon number of the alkyl group having 12 or more carbon atoms is 13 to 16, preferably 13.5 to 15.5.
  • the average carbon number is less than the lower limit value or exceeds the upper limit value, the low temperature viscosity characteristic of the lubricating oil composition becomes insufficient.
  • the average carbon number here means the average carbon number calculated based on the raw material methacrylate used for the synthesis
  • the weight average molecular weight of the poly (meth) acrylate pour point depressant is 10,000 to 200,000, preferably 30,000 to 180,000, more preferably 40,000 to 170,000.
  • the weight average molecular weight is less than the lower limit value or exceeds the upper limit value, the low temperature viscosity characteristic of the lubricating oil composition becomes insufficient.
  • the alkyl represented by the general formula (1) and R 2 is an alkyl having 20 or more carbon atoms.
  • the proportion of the structural unit as a group is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and particularly preferably 0 mol%. When the ratio exceeds the upper limit, the low temperature viscosity characteristic of the lubricating oil composition becomes insufficient.
  • a raw material monomer is prepared by selecting a (meth) acrylate represented by the following general formula (4) that satisfies R 2 as described above.
  • the raw material monomer can be obtained by polymerizing such that the weight average molecular weight satisfies the above conditions.
  • the raw material monomer may further contain a monomer other than (meth) acrylate represented by the following general formula (4).
  • the content ratio of (meth) acrylate represented by the general formula (4) is preferably 70 mol% or more, more preferably 80 mol% or more, based on the total amount of raw material monomers.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group.
  • the content of the poly (meth) acrylate pour point depressant according to this embodiment is preferably 0.01 to 2.0% by mass, more preferably 0.01 to 1.% by weight based on the total amount of the lubricating oil composition. It is 5% by mass, more preferably 0.01 to 1.0% by mass, and particularly preferably 0.01 to 0.75% by mass.
  • the content of the poly (meth) acrylate pour point depressant is less than the lower limit, the low temperature viscosity characteristics of the lubricating oil composition tend to be insufficient.
  • the upper limit is exceeded, the kinematic viscosity increases and the viscosity temperature characteristic deteriorates, and the energy saving characteristic tends to be lowered.
  • the lubricating oil composition according to this embodiment may contain any additive generally used in lubricating oils depending on the purpose in order to further improve its performance.
  • additives include pour point depressants other than poly (meth) acrylates according to this embodiment, metal detergents, ashless dispersants, antiwear agents (extreme pressure agents, oily agents, etc.), Examples include friction modifiers, viscosity index improvers, antioxidants, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, and antifoaming agents.
  • the content is preferably 0.01 to 10% by mass based on the total amount of the lubricating oil composition.
  • Kinematic viscosity at 100 ° C. of the lubricating oil composition according to the present embodiment is preferably 7.0 ⁇ 9.0mm 2 / s, more preferably 7.2 ⁇ 8.8mm 2 / s, more preferably 7.3 It is ⁇ 8.6 mm 2 / s, particularly preferably 7.3 to 8.5 mm 2 / s. If the kinematic viscosity at 100 ° C. is less than the lower limit, there is a risk of insufficient lubricity, and if it exceeds the upper limit, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
  • the kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present embodiment is preferably 28 to 40 mm 2 / s, more preferably 30 to 38 mm 2 / s, still more preferably 31 to 36 mm 2 / s, and particularly preferably. Is 32 to 35 mm 2 / s.
  • the kinematic viscosity at 40 ° C. is less than the lower limit, there is a risk of insufficient lubricity, and when it exceeds the upper limit, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained.
  • the viscosity index of the lubricating oil composition according to this embodiment is preferably 200 to 270, more preferably 220 to 265, still more preferably 230 to 260, and particularly preferably 240 to 258.
  • the viscosity index of the lubricating oil composition according to the present embodiment is less than the lower limit, low temperature viscosity and sufficient fuel saving performance may not be obtained. There is a risk of deterioration, and there is a risk of problems due to insufficient solubility of the additive and compatibility with the sealing material.
  • the MRV viscosity at ⁇ 40 ° C. of the lubricating oil composition according to this embodiment is preferably 10,000 to 60,000 mPa ⁇ s, more preferably 10,000 to 50,000 mPa ⁇ s, and still more preferably 15 15,000 to 40,000 mPa ⁇ s, particularly preferably 15,000 to 35,000 mPa ⁇ s.
  • the MRV viscosity here refers to the MRV viscosity specified in ASTM D4684. If the MRV viscosity at ⁇ 40 ° C. is less than the lower limit, there is a risk of insufficient lubricity, and if it exceeds the upper limit, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. There is.
  • the lubricating oil composition according to the present embodiment can achieve both a high viscosity index and a low temperature viscosity characteristic at a high level, it can be suitably used in various lubricating oil applications.
  • the lubricating oil composition is used in a gasoline engine for passenger cars, a gasoline engine for motorcycles, a diesel engine, a gas engine, a gas heat pump engine, a marine engine, a power generation engine, and the like. (Lubricating oil for internal combustion engines), automatic transmissions, manual transmissions, continuously variable transmissions, final reduction gears, etc.
  • Lubricating oils drive transmission device oils
  • shock absorbers hydraulic equipment for construction machinery, etc. Hydraulic oil, compressor oil, turbine oil, gear oil, refrigerating machine oil, oil for metal processing, and the like used in the above.
  • Polymethacrylates A to K shown in Table 1 were prepared.
  • Polymethacrylates A to K have a structural unit represented by the general formula (1).
  • R 1 is a methyl group
  • R 2 is an alkyl group having a specific number of carbon atoms in a specific ratio as shown in Table 1. It is what you have.
  • Table 1 a weight average molecular weight of polymethacrylate A ⁇ K, and also shows the average number of carbon atoms of the alkyl group having 12 or more carbon atoms of R 2.
  • an alkyl group having n carbon atoms is represented as Cn.
  • C1 means a methyl group.
  • Examples 1 to 10, Comparative Examples 1 to 15 In Examples 1 to 10 and Comparative Examples 1 to 15, lubrication having the compositions shown in Tables 3 to 7 using the polymethacrylates A to K shown in Table 1 and the lubricating base oil and additive package shown below. An oil composition was prepared. Tables 3 to 7 also show the kinematic viscosity and viscosity index at 100 ° C. of the lubricating oil composition.
  • An additive package A comprising an antiwear agent, a metal deactivator, an ashless dispersant, a metal detergent, a rust inhibitor and an antioxidant was used.

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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

L'invention concerne une composition d'huile lubrifiante comprenant : une huile de base d'huile lubrifiante dont la viscosité cinématique est comprise entre 3,5 et 4,5 mm2/s à 100 °C, l'indice de viscosité est supérieur ou égal à 145 et la valeur de produit d'addition d'urée est comprise entre 2 et 7 % en masse ; et un abaisseur de point d'écoulement de poly(méth)acrylate comprenant des motifs structuraux représentés par la formule (1). En ce qui concerne la quantité totale desdits motifs structuraux représentés par la formule (1) et inclus dans ledit abaisseur de point d'écoulement de poly(méth)acrylate, le pourcentage de motifs structuraux qui sont représentés par la formule (1) et dans lesquels R2 représente un groupe méthyle est compris entre 0 et 10 % mol, et le pourcentage de motifs structuraux qui sont représentés par la formule (1) et dans lesquels les R2 respectifs représentent des groupes alkyle avec des nombres d'atomes de carbone supérieurs ou égaux à 12 est compris entre 90 et 100 % mol. Le nombre moyen d'atomes de carbone desdits groupes alkyle avec des nombres d'atomes de carbone supérieurs ou égaux à 12 est compris entre 13 et 16. Le poids moléculaire moyen en poids desdits abaisseurs de point d'écoulement de poly(méth)acrylate est compris entre 10 000 et 200 000. (Dans la formule (1), R1 représente un atome d'hydrogène ou un groupe méthyle, et R2 représente un groupe alkyle.)
PCT/JP2014/058632 2013-03-29 2014-03-26 Composition d'huile lubrifiante WO2014157383A1 (fr)

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JP6420964B2 (ja) * 2014-03-31 2018-11-07 出光興産株式会社 内燃機関用潤滑油組成物
JP6905971B2 (ja) * 2016-02-25 2021-07-21 出光興産株式会社 鉱油系基油、及び潤滑油組成物
US20220298444A1 (en) * 2019-06-14 2022-09-22 Basf Se A lubricant with a polyacrylate based on c13/15 acrylate

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US20160053196A1 (en) 2016-02-25

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