HK1019891B - LUBRICATING OIL COMPRISING RANDOM COPOLYMER OFα-OLEFIN/AROMATIC VINYL COMPOUND - Google Patents
LUBRICATING OIL COMPRISING RANDOM COPOLYMER OFα-OLEFIN/AROMATIC VINYL COMPOUND Download PDFInfo
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Description
Technical Field
The present invention relates to lubricating oils. More particularly, the present invention relates to a lubricating oil comprising an α -olefin/aromatic vinyl compound random copolymer.
Background
Lubricating base oils comprising mineral oils or synthetic oils such as ethylene/alpha-olefin copolymers contained in petroleum oils have hitherto been known. Further, lubricating oil compositions comprising a viscosity index improver or a lubricating oil additive each containing an α -olefin polymer are also known.
It is desirable that lubricating base oils have not only excellent viscosity properties (particularly low temperature fluidity) but also excellent thermal stability, oxidation stability and lubricating properties.
Lubricating base oils may be blended with additives such as extreme pressure additives (extreme pressure agents), but lubricating base oils, particularly hydrocarbon synthetic oils, are generally poorly compatible with lubricating oil additives, and thus the type and amount of viscosity index improvers or lubricating oil improvers added to lubricating oils is significantly limited.
Lubricating oil compositions in which esters are added as compatibility improvers to improve the compatibility between the lubricating base oil and the lubricating oil additives are known.
Even lubricating oil compositions comprising viscosity index improvers or compatibility improvers are needed to further improve thermal stability, oxidation stability, lubricating properties and compatibility with lubricating oil additives. Furthermore, there is a need for a lubricating base oil having sufficient compatibility with lubricating oil additives (even when a compatibility improver is not used).
In addition, when middle distillate fuel oils such as gas oil (light oil) and heavy oil are used or stored at low temperatures, crystals of wax contained in the oils are gradually formed. If the oil containing the wax crystals formed is used, problems such as clogging (clogging) of pipes and the viscosity of the entire oil is so high that the flow of the oil is difficult, etc. may occur. To solve these problems, a method of adding a fluidity improver such as an ethylene/α -olefin copolymer to a middle distillate fuel oil is known.
It is also known to reduce the clogging point (CFPP) of low-temperature filters by adding to the middle distillate fuel oil a polybutadiene having hydroxyl end groups and containing not less than 70% of 1, 2-bonds or hydrides thereof.
For the purification of automobile exhaust gases, low-sulfur gas oils, which are low-sulfur diesel fuels, are often used, and the legal provisions impose strict restrictions on this. However, sulfur in fuel oil imparts lubricating properties to the fuel oil, and if the content of sulfur in fuel oil is reduced, the lubricating properties of the fuel oil tend to be reduced, thereby causing wear of the fuel nozzle. Therefore, there is also a need for fuel oil flow improvers having excellent lubricating properties.
The present invention has been made in view of such circumstances as described above, and therefore it is an object of the present invention to provide a lubricating oil and a lubricating oil composition each having not only excellent compatibility with lubricating oil additives but also excellent viscosity properties, thermal stability, oxidation stability and lubricating properties.
It is another object of the present invention to provide a lubricating oil composition having excellent properties, which comprises a base oil composed of a mineral oil and/or a hydrocarbon synthetic oil and a viscosity index improver comprising a specific α -olefin/aromatic vinyl compound random copolymer.
It is still another object of the present invention to provide a lubricating oil composition having excellent properties, which comprises a base oil composed of a mineral oil and/or a hydrocarbon synthetic oil, a compatibility improver comprising a specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer, and a lubricating oil additive.
It is still another object of the present invention to provide a viscosity index improver comprising a specific α -olefin/aromatic vinyl compound random copolymer, and a lubricating oil compatibility improver comprising a specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer.
Summary of the invention
The lubricating oil of the present invention comprises an α -olefin/aromatic vinyl compound random copolymer comprising:
40 to 75 mol% of constituent units derived from ethylene,
0 to 45 mol% of a constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms, and
1 to 40 mol% of a constituent unit derived from an aromatic vinyl compound,
provided that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%,
the alpha-olefin/aromatic vinyl compound random copolymer has an intrinsic viscosity [ eta ] of 0.01 to 0.50dl/g as measured in decalin at 135 ℃.
The first lubricating oil composition of the present invention comprises an alpha-olefin/aromatic vinyl compound random copolymer and a lubricating oil additive.
When an alpha-olefin/aromatic vinyl compound random copolymer is used as a lubricating base oil in admixture with at least one additive selected from the group consisting of an extreme pressure additive, an anti-wear agent, an oiliness improver and a detergent dispersant, a lubricating oil composition having excellent properties can be obtained.
The second lubricating oil composition of the present invention comprises:
a base oil comprising a mineral oil and/or a hydrocarbon synthetic oil, and
an alpha-olefin/aromatic vinyl compound random copolymer comprising 40 to 75 mol% of a constituent unit derived from ethylene, 0 to 45 mol% of a constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms and 1 to 40 mol% of a constituent unit derived from an aromatic vinyl compound, provided that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%, said random copolymer having an intrinsic viscosity [ eta ] of 0.1 to 5.0dl/g as measured in decalin at 135 ℃.
The third lubricating oil composition of the present invention comprises:
a base oil comprising a mineral oil and/or a hydrocarbon synthetic oil,
a low molecular weight alpha-olefin/aromatic vinyl compound random copolymer and a lubricating oil additive, the random copolymer comprising 40 to 75 mol% of a constituent unit derived from ethylene, 0 to 45 mol% of a constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms and 1 to 40 mol% of a constituent unit derived from an aromatic vinyl compound, with the proviso that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%, the random copolymer having an intrinsic viscosity [ eta ] of 0.01 to 0.30dl/g as measured in decalin at 135 ℃.
The viscosity index improver of the present invention comprises the same α -olefin/aromatic vinyl compound random copolymer as the specific α -olefin/aromatic vinyl compound random copolymer used in the second lubricating oil composition.
The lubricating oil compatibility improver of the present invention comprises the same low-molecular-weight α -olefin/aromatic vinyl compound random copolymer as the specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer used in the third lubricating oil composition.
The fuel oil composition of the present invention comprises:
middle distillate fuel oils having a boiling point of from 150 to 400 ℃, and
an alpha-olefin/aromatic vinyl type fuel oil flowability improver comprising an alpha-olefin/aromatic vinyl compound random copolymer which comprises 60 to 90 mol% of a constituent unit derived from ethylene, 0 to 39 mol% of a constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms and 1 to 40 mol% of a constituent unit derived from an aromatic vinyl compound, with the proviso that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%, and which has an intrinsic viscosity [ eta ] measured in decalin at 135 ℃ of 0.01 to 1.0 dl/g.
Best Mode for Carrying Out The Invention
The lubricating oil, lubricating oil composition, viscosity index improver, lubricating oil compatibility improver and fuel oil composition of the present invention will be described in detail below.
The lubricating oil of the present invention is described first.
The lubricating oil of the present invention comprises an α -olefin/aromatic vinyl compound random copolymer obtained from ethylene, an aromatic vinyl compound and optionally an α -olefin having 3 to 20 carbon atoms.
Alpha-olefin/aromatic vinyl compound random copolymer
The α -olefin/aromatic vinyl compound random copolymer used in the present invention is a random copolymer of ethylene and an aromatic vinyl compound (ethylene/aromatic vinyl compound random copolymer) or a random copolymer of ethylene, an α -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound (ethylene/α -olefin/aromatic vinyl compound random copolymer).
In the ethylene/aromatic vinyl compound random copolymer, the amount of the constituent unit derived from ethylene is from 60 to 75 mol%, preferably from 60 to 70 mol%, and the amount of the constituent unit derived from the aromatic vinyl compound is from 25 to 40 mol%, preferably from 30 to 40 mol%.
Examples of the aromatic vinyl compound include styrene; mono-or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene and divinylbenzene; 3-phenylpropylene; 4-phenylbutene; and alpha-methylstyrene. Among them, styrene or 4-methoxystyrene is preferred.
In the ethylene/aromatic vinyl compound random copolymer, an α -olefin other than ethylene and a vinyl aromatic compound may be copolymerized. Examples of such alpha-olefins include alpha-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene. Among them, preferred is propylene, 1-butene, 1-pentene, 1-hexene or 1-octene. These alpha-olefins may be used alone or in combination of two or more.
In the ethylene/alpha-olefin/aromatic vinyl compound random copolymer, the amount of the constituent unit derived from ethylene is 40 to 75 mol%, the amount of the constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms is not more than 45 mol%, and the amount of the constituent unit derived from an aromatic vinyl compound is 1 to 40 mol%, provided that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%. It is preferable that the amount of the constituent unit derived from ethylene is 40 to 70 mol%, the amount of the constituent unit derived from an α -olefin having 3 to 20 carbon atoms is not more than 40 mol%, and the amount of the constituent unit derived from an aromatic vinyl compound is 1 to 30 mol%, provided that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an α -olefin is 70 to 99 mol%.
When the amount of the constituent unit derived from ethylene, the amount of the constituent unit derived from an α -olefin having 3 to 20 carbon atoms and the amount of the constituent unit derived from an aromatic vinyl compound are within the above ranges, a lubricating base oil having a good balance of properties in terms of various properties such as viscosity properties, heat resistance and lubricating properties can be obtained.
Among such copolymers as described above, preferred is an α -olefin/aromatic vinyl compound random copolymer in which the total amount of constituent units derived from an α -olefin having 3 to 20 carbon atoms and constituent units derived from an aromatic vinyl compound is from 0.1 to 40 mol%.
In the α -olefin/aromatic vinyl compound random copolymer, other monomers such as a non-conjugated diene may be copolymerized. Examples of the non-conjugated diene include 1, 4-pentadiene, 1, 4-hexadiene, 4-methyl-1, 5-heptadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 2, 5-norbornadiene, 1, 6-cyclooctadiene, 2-ethylidene-2, 5-norbornadiene, 2-isopropenyl-2, 5-norbornadiene, dicyclopentadiene, 1, 6-octadiene, 1, 7-octadiene, tricyclopentadiene, and esters of dihydrodicyclopentadienoxyethyleneand unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid). These non-conjugated dienes may be used alone or in combination of two or more.
The alpha-olefin/aromatic vinyl compound random copolymer has an intrinsic viscosity [ eta ] of 0.01 to 0.50dl/g, preferably 0.02 to 0.40dl/g, as measured in decalin at 135 ℃.
In the α -olefin/aromatic vinyl compound random copolymer used in the present invention, it is desirable that the ratio of the constituent unit forming the two constituent unit sequences derived from the aromatic vinyl compound to all the constituent units derived from the aromatic vinyl compound is not more than 1%, preferably not more than 0.1%. The ratio of the two sequences of constituent units from the aromatic vinyl compound may be determined by13C-NMR measurement.
The process for producing the α -olefin/aromatic vinyl compound random copolymer is described below.
The lubricating oil containing the alpha-olefin/aromatic vinyl compound random copolymer of the present invention has excellent compatibility with additives, as well as excellent viscosity properties, thermal stability, oxidation stability and wear resistance.
Next, the first lubricating oil composition of the present invention will be described.
The first lubricating oil composition of the invention comprises a lubricating base oil comprising the same α -olefin/aromatic vinyl compound random copolymer as used to form the above-described lubricating oil and a lubricating oil additive.
Lubricating oil additive
The lubricating oil additive used in the present invention is at least one additive selected from the group consisting of an extreme pressure additive, an anti-wear agent, an oiliness improver and a detergent dispersant.
Examples of extreme pressure additives include sulfur-type extreme pressure additives such as sulfides, sulfoxides, sulfones, thiophosphonates, thiocarbonates, fats and oils, sulfurized fats and oils, and olefin sulfides; phosphoric acids, such as phosphoric esters, phosphorous esters (phosphous esters), phosphoesteramines and phosphoesteramines; and halogenated compounds such as chlorinated hydrocarbons.
Examples of anti-wear agents include inorganic or organic molybdenum compounds, such as molybdenum disulfide; organoboron compounds, such as alkyl thiol borate esters; graphite; antimony sulfide; a boron compound; and polytetrafluoroethylene.
Examples of the oiliness improver include higher fatty acids such as oleic acid and stearic acid; higher alcohols such as oleyl alcohol; an amine; an ester; sulfurized fats and oils; and chlorinated fats and oils.
Examples of detergent dispersants include metal sulfonates such as calcium sulfonate, magnesium sulfonate and barium sulfonate; a thiophosphonate salt; a phenolate salt; a salicylate; a succinimide; benzylamine; and a succinate salt.
The first lubricating oil composition of the present invention may further comprise a viscosity index improver, an antioxidant, a preservative and a defoaming agent.
As the viscosity index improver, those commonly added to lubricating oils may be used, and examples thereof include natural resins such as mineral oils, and synthetic resins such as ethylene/α -olefin copolymers, α -olefin homopolymers, styrene/butadiene copolymers, condensates of poly (meth) acrylates and naphthalenes.
Examples of the antioxidant include amine compounds such as 2, 6-di-tert-butyl-4-methylphenol; and sulfur or phosphorus compounds, such as zinc dithiophosphate.
Examples of preservatives include carboxylic acids and salts thereof, such as oxalic acid; a sulfonate salt; an ester; an alcohol; phosphoric acid and its salts; benzotriazole and derivatives thereof; and thiazole compounds.
Examples of the defoaming agent include silicone compounds such as dimethylsiloxane and silica gel dispersion; an alcohol compound; and an ester compound.
Although the amount of the lubricating oil additive to be used varies depending on the desired lubricating property, the amount is usually 0.01 to 80 parts by weight, preferably 0.05 to 60 parts by weight, based on 100 parts by weight of the α -olefin/aromatic vinyl compound random copolymer.
The lubricating oil composition of the present invention may also comprise mineral or hydrocarbon synthetic oils in amounts up to 50 wt.%.
Since the first lubricating oil composition of the present invention comprises an α -olefin/aromatic vinyl compound random copolymer as a base oil, the composition has excellent compatibility with additives as well as excellent viscosity properties, thermal stability, oxidation stability and wear resistance.
Next, a second lubricating oil composition and viscosity index improver of the invention will be described.
The second lubricating oil composition of the present invention comprises a base oil comprising a mineral oil and/or a hydrocarbon synthetic oil and a specific alpha-olefin/aromatic vinyl compound random copolymer which functions as a viscosity index improver.
The viscosity index improver of the present invention comprises the same α -olefin/aromatic vinyl compound random copolymer as used in the second lubricating oil composition of the present invention.
Base oil
The base oil used in the second lubricating oil composition of the present invention is a lubricating base oil comprising a mineral oil and/or a hydrocarbon synthetic oil. These oils may be used singly or in the form of a mixture of two or more kinds, and there is no particular limitation so long as they have a viscosity of 1.5 to 40.0mm at 100 ℃2(ii) S, preferably 2.0 to 10.0mm2/S。
The viscosity of the mineral oil is within the above range.
The mineral oil may be, for example, a refined oil obtained by refining the resulting distilled oil in a conventional manner after subjecting a paraffinic crude oil or a middle base crude oil to atmospheric distillation or subjecting a residue of atmospheric distillation to vacuum distillation, or may be a deep dewaxed oil obtained after subjecting the above-obtained refined oil to deep dewaxing. Examples of refining processes include hydrogenation, dewaxing, solvent extraction, base distillation, sulfuric acid washing and clay treatment. These methods may be used alone or in appropriate combination, or the same method may be repeated a plurality of times. In these cases, the order of the method and the number of repetitions are not particularly limited. In the present invention, it is particularly preferable to use a mineral oil obtained by a solvent dewaxing method or a deep dewaxing method conducted under severe conditions, such as a catalytic hydrodewaxing method using a zeolite catalyst.
Examples of hydrocarbon synthetic oils which may be suitably used include oligomers obtained by polymerizing or copolymerizing olefins having 2 to 20 carbon atoms or any mixture of these olefins, such as 1-octene oligomers, 1-decene oligomers and 1-dodecene oligomers. In addition to mineral oils and/or hydrocarbon synthetic oils, diesters may also be used, such as di (2-ethylhexyl) sebacate, dioctyl adipate and dioctyl dodecanoate, and polyol esters, such as pentaerythritol tetraoleate and trimethylolpropane trinonanoate.
The oligomers can be obtained by (co) polymerizing olefins containing from 2 to 20 carbon atoms by conventional methods.
In the second lubricating oil composition of the present invention, the base oil is used in an amount of 50.0 to 99.8% by weight, preferably 60.0 to 95.0% by weight.
Alpha-olefin/aromatic vinyl compound random copolymer
In the second lubricating oil composition of the present invention, a specific α -olefin/aromatic vinyl compound random copolymer which functions as a viscosity index improver is used as the base oil or the viscosity index improver. This copolymer is similar to the α -olefin/aromatic vinyl compound random copolymer forming the above-mentioned lubricating oil or the first lubricating oil composition of the present invention, and is a random copolymer of ethylene and an aromatic vinyl compound (ethylene/aromatic vinyl compound random copolymer) or a random copolymer of ethylene, an α -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound (ethylene/α -olefin/aromatic vinyl compound random copolymer).
However, the alpha-olefin/aromatic vinyl compound random copolymer used in the second lubricating oil composition of the present invention has an intrinsic viscosity (. eta.) of 0.1 to 5.0dl/g, preferably 0.5 to 3.0dl/g, as measured in decalin at 135 ℃.
The amount of the α -olefin/aromatic vinyl compound random copolymer which functions as a viscosity index improver is 1.0 to 50.0 parts by weight, preferably 2.0 to 30.0 parts by weight, based on 100 parts by weight of the base oil.
The second lubricating oil composition of the present invention has excellent lubricating oil properties because the base oil comprising a mineral oil and/or a hydrocarbon synthetic oil is blended with an α -olefin/aromatic vinyl compound random copolymer which functions as a base oil or a viscosity index improver.
Next, the third lubricating oil composition and the lubricating oil compatibility improver of the present invention will be described.
The third lubricating oil composition of the present invention comprises a base oil comprising a mineral oil and/or a hydrocarbon synthetic oil, a specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer serving as a compatibility improver, and a lubricating oil additive.
The lubricating oil compatibility improver of the present invention is the same α -olefin/aromatic vinyl compound random copolymer as used to form the third lubricating oil composition of the present invention.
Base oil
Examples of the base oil include the above-mentioned mineral oils and hydrocarbon synthetic oils used as the base oil of the second lubricating oil composition.
Alpha-olefin/aromatic vinyl compound random copolymer
In the third lubricating oil composition of the present invention, a specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer which functions as a compatibility improver is used. This copolymer is similar to the α -olefin/aromatic vinyl compound random copolymer forming the above-mentioned lubricating oil or the first lubricating oil composition of the present invention, and is a random copolymer of ethylene and an aromatic vinyl compound (ethylene/aromatic vinyl compound random copolymer) or a random copolymer of ethylene, an α -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound (ethylene/α -olefin/aromatic vinyl compound random copolymer). However, the low-molecular weight α -olefin/aromatic vinyl compound random copolymer used in the third lubricating oil composition of the present invention has an intrinsic viscosity (. eta.) of 0.01 to 0.30dl/g, preferably 0.01 to 0.20dl/g, as measured in decalin at 135 ℃.
The lubricating oil additive can be easily dissolved in the base oil due to the use of the low-molecular-weight α -olefin/aromatic vinyl compound random copolymer which functions as a compatibility improver.
The amount of the α -olefin/aromatic vinyl compound random copolymer which functions as a compatibility improver is from more than 0 part by weight to not more than 50 parts by weight, preferably from more than 0 part by weight to not more than 30 parts by weight, based on 100 parts by weight of the base oil.
The weight ratio of the low-molecular weight α -olefin/aromatic vinyl compound random copolymer to the lubricating oil additive is from 0.01 to 4.0, preferably from 0.01 to 2.0.
Lubricating oil additive
The third lubricating oil composition of the present invention comprises a lubricating oil additive such as the aforementioned extreme pressure additive, anti-wear agent, oiliness improver, detergent dispersant, antioxidant, preservative or antifoaming agent.
Although the amount of the lubricating oil additive used varies depending on the desired lubricating properties, the amount is usually 0.01 to 50% by weight, preferably 0.05 to 30% by weight, based on the lubricating oil composition.
The third lubricating oil composition of the present invention has excellent lubricating oil properties because the base oil comprising a mineral oil and/or a hydrocarbon synthetic oil is blended with a lubricating oil additive and a low-molecular-weight α -olefin/aromatic vinyl compound random copolymer which functions as a base oil or a compatibility improver.
Next, a method for producing an α -olefin/aromatic vinyl compound random copolymer will be described.
The (low molecular weight) α -olefin/aromatic vinyl compound random copolymer used in the present invention can be obtained by copolymerizing ethylene, an aromatic vinyl compound, and if necessary, an α -olefin having 3 to 20 carbon atoms in the presence of, for example, a metallocene catalyst (a).
As the metallocene catalyst (a), various metallocene-type catalysts, such as those currently used as single site catalysts and catalysts similar thereto, can be used without particular limitation. In particular, it is preferable to use a catalyst comprising a metallocene compound (b) of a transition metal (transition metal compound) and an organoaluminum oxy-compound (c) and/or an ionized ionic compound (d).
The metallocene compound (b) may be, for example, a metallocene compound selected from transition metals of group 4 of the periodic table (long form periodic table) of elements represented by groups 1 to 18 in IUPAC inorganic nomenclature, revised edition (1989), particularly a metallocene compound represented by the following formula (1).
MLx (1)
In formula (1), M is a transition metal selected from group 4 elements of the periodic table, such as zirconium, titanium or hafnium, and x is the valence of the transition metal.
L is a ligand coordinated to the transition metal. At least one ligand L is a ligand having a cyclopentadienyl skeleton which may have a substituent.
Examples of the ligands having a cyclopentadienyl skeleton include alkyl-or cycloalkyl-substituted cyclopentadienyl groups such as cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-or isopropylcyclopentadienyl group, n-, i-, s-or t-butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group and methylcyclohexylcyclopentadienyl group.
Furthermore, indenyl, 4, 5, 6, 7-tetrahydroindenyl and fluorenyl are also possible.
These groups may be substituted with a halogen atom or a trialkylsilyl group.
Among the above ligands, particularly preferred is an alkyl-substituted cyclopentadienyl group.
When the compound represented by the formula (1) contains two or more cyclopentadienyl skeleton-containing ligands L, the two cyclopentadienyl skeleton-containing ligands may be linked to each other through an alkylene group such as ethylene or propylene, a substituted alkylene group such as isopropylene and diphenylmethylene, silylene, or a substituted silylene group such as dimethylsilylene, diphenylsilylene or methylphenylsilylene.
Examples of L other than the ligand having cyclopentadienyl skeleton include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfonic acid groups (-SO)3R1) A halogen atom or a hydrogen atom, wherein R1Is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group.
Examples of the hydrocarbon group having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups, more specifically:
alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl and dodecyl;
cycloalkyl groups such as cyclopentyl and cyclohexyl;
aryl groups such as phenyl and tolyl; and
aralkyl groups such as benzyl and neo phenyl (neophyl).
Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy and octyloxy.
Aryloxy is, for example, phenoxy.
Containing sulfonic acid groups (-SO)3R1) Examples of (B) include methanesulfonyloxy (methanesulfonato), p-toluenesulfonyloxy, trifluoromethanesulfonyl (trifluoromethanesulfonato) and p-chlorobenzenesulfonyloxy.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
The metallocene compound (b) of the above formula (1) in which the valence of the transition metal is 4 can be more specifically represented by the following formula (2):
R2 kR3 lR4 mR5 nM (2)
wherein M is the above-mentioned transition metal, preferably zirconium or titanium, R2Is a group (ligand) containing a cyclopentadienyl skeleton, R3，R4And R5Each of which may be the same or different, is a group having a cyclopentadienyl skeleton or the same group as other L except for the ligand having a cyclopentadienyl skeleton in the above formula (1), k is an integer of not less than 1, and k + L + m + n ═ 4.
In the present invention, a compound represented by the following formula (3) may also be used as the metallocene compound (b).
L1M2Z1 2 (3)
Wherein M is2A metal that is a metal of group 4 of the periodic table or a lanthanide;
L1derivatising groups with delocalised pi-bonded groups, which derivatise the metal M2The active center has a constrained geometry; and
two Z1Which may be the same or different, are each hydrogen, halogen, a hydrocarbon group of 20 or less carbon atoms, a silicon or germanium atom, a silyl group or a germyl group.
Of the metallocene compounds (b) represented by the formula (3), preferred are those represented by the following formula (4).
In formula (4), M3Is titanium, zirconium or hafnium, Z1As defined above.
CpIs eta is5Bonding mode pi bonding to M3Substituted cyclopentadienyl or derivative thereof.
W1Is oxygen, sulfur, boron, an element of group 14 of the periodic table or a group containing any of these elements.
V1Are ligands containing nitrogen, phosphorus, oxygen or sulfur.
W1And V1May together form a fused ring. And, CpAnd W1May together form a fused ring.
Represented by formula (4) wherein CpExamples of preferred groups include cyclopentadienyl, indenyl, fluorenyl and saturated derivatives of these groups. These radicals or derived radicals together with the metal atom (M)3) Together forming a ring.
Each carbon atom in the cyclopentadienyl group may be substituted or unsubstituted by the same or different groups selected from the group consisting of a hydrocarbon group, a substituted hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, a metalloid selected from the group consisting of a metalloid group substituted with a hydrocarbon group of group 14 of the periodic table, and a halogen atom. In addition, two or more substituents may together form a fused ring. Preferred hydrocarbyl and substituted hydrocarbyl groups which may be substituted for at least one hydrogen atom of the cyclopentadienyl group contain from 1 to 20 carbon atoms and include straight and branched chain alkyl, cycloalkyl, alkyl-substituted cycloalkyl, aryl and alkyl-substituted aryl groups. Examples of preferred organometalloid radicals include mono-, di-and tri-substituted organometalloid radicals of group 14 elements, each of which contains from 1 to 20 carbon atoms. Specific examples of preferred organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl, triphenylgermyl and trimethylgermyl.
In formula (4) by Z1Examples of groups represented include hydrido (hydrido), halo, alkyl, silyl, germyl, aryl, (acyl) amino, aryloxy, alkoxy, phosphido (phosphinido), sulfido (sulfido), acyl, pseudohalo (pseudo-halido) (e.g., cyanide, azido), acetylacetonate (acetylacetonato) and mixtures thereof. From Z1The groups represented may be the same or different from each other.
As the metallocene compound (b), the metallocene compound represented by the formula (3) is particularly preferable from the viewpoints of polymerization activity and transparency, rigidity, heat resistance and impact resistance of the resulting molded product. The above metallocene compounds (b) may be used singly or in combination of two or more.
The metallocene compounds (b) used in the present invention may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.
Next, the organoaluminum oxy-compound (c) and the ionized ionic compound (d) used for forming the metallocene catalyst (a) will be described.
The organoaluminum oxy-compound (c) used in the present invention may be conventionally known aluminoxane (aluminoxane) or a benzene-insoluble organoaluminum oxy-compound (c) exemplified in Japanese patent laid-open publication No. 78687/1990.
Aluminoxanes can be prepared, for example, by the process described below and are generally recovered as a hydrocarbon solvent solution.
(1) An organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent suspension of a compound containing adsorption water or a salt containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerium chloride hydrate to react the organoaluminum compound with the adsorption water or the water of crystallization, followed by recovering an aromatic hydrocarbon solvent solution of aluminoxane.
(2) Water, ice or water vapor is allowed to act directly on an organoaluminum compound (e.g., trialkylaluminum) in a medium (e.g., benzene, toluene, diethyl ether or tetrahydrofuran), followed by recovering an aromatic hydrocarbon solvent solution of aluminoxane.
(3) An organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a hydrocarbon medium such as decane, benzene or toluene.
Examples of the ionized ionic compound (d) include Lewis acids, ionic compounds, borane compounds and carborane compounds. These ionized ionic compounds are described in national publications of international patents 501950/1989 and 502036/1989, japanese laid-open patent publication nos. 179005/1991, 179006/1991, 207703/1991 and 207704/1991 and U.S. patent No. 5,321,106.
Lewis acids which can be used as ionizing ionic compounds (d) may be, for example, those of the formula BR3(each R is the same or different and is a phenyl group which may have a substituent such as fluorine, methyl or trifluoromethyl, or a fluorine atom). Examples of such compounds include boron trifluoride, triphenylboron, tris (4-fluorophenyl) boron, tris (3, 5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron and tris (pentafluorophenyl) boron.
The ionic compound that can be used as the ionized ionic compound (d) is a salt comprising a cationic compound and an anionic compound. The anionic compound reacts with the metallocene compound (b) to make the compound (b) cationic and form an ion pair, so that the transition metal cation species are stabilized. Examples of such anions include organoboron compound anions, organoarsenic compound anions and organoaluminum compound anions. Preferred are anions which are relatively bulky and which are capable of stabilizing the transition metal cation species. Examples of cations include metal cations, organometallic cations, carbonium cations, tripium cations, oxonium cations, sulfonium cations, phosphonium cations and ammonium cations. More specifically, there may be triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium (ferrocenium) cation, etc.
Among them, preferred are ionic compounds containing a boron compound as an anionic compound, and examples thereof include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts.
Examples of the trialkyl-substituted ammonium salts include triethylammoniumtetra (phenyl) boron, tripropylammoniumtetra (phenyl) boron, tri (n-butyl) ammoniumtetra (phenyl) boron and trimethylammonium tetra (p-tolyl) boron.
Examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetrakis (phenyl) boron.
Examples of the dialkylammonium salts include di (n-propyl) ammonium tetrakis (pentafluorophenyl) boron and dicyclohexylammonium tetrakis (phenyl) boron.
Examples of triarylphosphonium salts include triphenylphosphonium tetrakis (phenyl) boron, tris (methylphenyl) phosphonium tetrakis (phenyl) boron and tris (dimethylphenyl) phosphonium tetrakis (phenyl) boron.
Also useful as ionic compounds are triphenylcarbeniumtetrakis (pentafluorophenyl) borate, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate and ferroceniumtetrakis (pentafluorophenyl) borate.
Examples of the borane compounds that can be used as the ionized ionic compound (d) include decaborane (14); anionic salts such as bis [ tri (n-butyl) ammonium ] nonaborate and bis [ tri (n-butyl) ammonium ] decaborate; and salts of metallic borane anions such as tri (n-butyl) ammonium bis (dodecahydrododecaborate) cobaltate (III) and bis (tri (n-butyl) ammonium bis (dodecahydrododecaborate) nickelate (III).
Examples of carborane compounds that can be used as the ionizing ionic compound (d) include anionic salts such as 4-carbanonaborane (14) and 1, 3-dicarbanonaborane (13); and metal carborane anion salts such as tri (n-butyl) ammonium bis (nonahydro-1, 3-dicarbanonaborate) cobaltate (III) and tri (n-butyl) ammonium bis (undecahydrido-7, 8-dicarbaundecaborate) ferrate (III).
The above-mentioned ionizing ionic compounds (d) may be used singly or in combination of two or more.
The metallocene catalyst (a) used in the present invention may optionally contain the following organoaluminum compound (e) in addition to the above components.
The organoaluminum compound (e) optionally used may be, for example, an organoaluminum compound represented by the following formula (5):
(R6)nAlX3-n (5)
wherein R is6Is a hydrocarbon group of 1 to 15 carbon atoms (preferably 1 to 4 carbon atoms), X is a halogen atom or hydrogen, and n is 1 to 3.
The hydrocarbon group having 1 to 15 carbon atoms may be, for example, an alkyl group, a cycloalkyl group or an aryl group. Examples of such groups include methyl, ethyl, n-propyl, isopropyl and isobutyl.
Examples of the organoaluminum compound include:
trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and tri-sec-butylaluminum;
represented by the formula (i-C)4H9)xAly(C5H10)z(wherein x, y and z are each a positive number, and z.gtoreq.2x), such as isoprenylaluminum;
dialkylaluminum halides such as dimethylaluminum chloride and diisobutylaluminum chloride;
dialkylaluminum hydrides, such as diisobutylaluminum hydride;
dialkylaluminum alkoxides such as dimethylaluminum methoxide; and
dialkylaryloxyaluminums, such as diethylphenoxyaluminum.
The copolymerization of ethylene, an aromatic vinyl compound and, if desired, an alpha-olefin having 3 to 20 carbon atoms can be carried out batchwise or continuously. When the copolymerization is carried out continuously, the metallocene catalyst (a) is used in the following concentration.
The concentration of the metallocene compound (b) in the polymerization system is usually 0.00005 to 0.1mmol/l (polymerization volume), preferably 0.0001 to 0.05 mmol/l.
The organoaluminum oxy-compound (c) is used in such an amount that the ratio of the aluminum atom in the organoaluminum oxy-compound to the transition metal of the metallocene compound (b) in the polymerization system becomes 0.1 to 10,000, preferably 1 to 5,000.
The amount of the ionized ionic compound (d) to be used is such that the molar ratio of the ionized ionic compound (d) to the metallocene compound (b) in the polymerization system (ionized ionic compound (d)/metallocene compound (b)) is from 0.1 to 20, preferably from 1 to 10.
The organoaluminum compound (e) is used in such an amount that the concentration of the organoaluminum compound (e) becomes usually 0 to 5mmol/l (polymerization volume), preferably 0 to 2 mmol/l.
The copolymer reaction for producing the alpha-olefin/aromatic vinyl compound random copolymer is carried out at a temperature of usually-30 to +250 ℃, preferably 0 to 200 ℃, and usually more than 0 but not more than 80kg/cm2(gauge pressure), preferably more than 0 but not more than 50kg/cm2(gauge pressure).
The reaction time (average residence time in the case of continuous copolymerization) although it varies depending on the reaction conditions such as catalyst concentration and polymerization temperature, is usually from 5 minutes to 3 hours, preferably from 10 minutes to 1.5 hours.
In the preparation of the α -olefin/aromatic vinyl compound random copolymer, ethylene, an aromatic vinyl compound and optionally an α -olefin having 3 to 20 carbon atoms are added to the polymerization system in such amounts as to obtain a copolymer having the above-mentioned specific composition. In the copolymerization, a molecular weight regulator such as hydrogen may be added.
When ethylene, an aromatic vinyl compound and optionally an α -olefin having 3 to 20 carbon atoms are copolymerized as described above, a polymerization solution containing an α -olefin/aromatic vinyl compound random copolymer is generally obtained. The polymerization solution is treated in a conventional manner to obtain an α -olefin/aromatic vinyl compound random copolymer.
Next, the fuel oil composition of the present invention will be described.
The fuel oil composition of the present invention comprises:
a fuel oil of a middle distillate boiling at 150-
An alpha-olefin/aromatic vinyl compound random copolymer obtained from ethylene, an aromatic vinyl compound and optionally an alpha-olefin having 3 to 20 carbon atoms.
Middle distillate fuel oil
The boiling point of the fuel oil of the middle distillate used in the present invention is 150-400 ℃, and the typical example of the fuel oil of the middle distillate is gas oil or fuel oil A. Particularly preferred is a middle distillate fuel oil having a 90% running point (running point) to initial boiling point difference of not less than 110 ℃ and, for example, not more than 200 ℃, preferably 115 ℃ and 190 ℃, and a cold filter plugging point of-10 ℃ to +10 ℃.
The middle distillate fuel oil may be used alone or as a mixture of two or more.
Alpha-olefin/aromatic vinyl compound random copolymer
In the present invention, the α -olefin/aromatic vinyl compound random copolymer can be used as a fluidity improver for fuel oil. The copolymer is a random copolymer of ethylene and an aromatic vinyl compound (ethylene/aromatic vinyl compound random copolymer) or a random copolymer of ethylene, an α -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound (ethylene/α -olefin/aromatic vinyl compound random copolymer).
In the ethylene/aromatic vinyl compound random copolymer, the amount of the constituent unit derived from ethylene is from 60 to 90 mol%, preferably from 65 to 85 mol%, and the amount of the constituent unit derived from the aromatic vinyl compound is from 10 to 40 mol%, preferably from 15 to 35 mol%.
Examples of the aromatic vinyl compound include styrene; mono-or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene and divinylbenzene; 3-phenylpropylene; 4-phenylbutene; and alpha-methylstyrene. Among them, styrene or 4-methoxystyrene is preferred.
In the ethylene/aromatic vinyl compound random copolymer, an α -olefin other than ethylene and a vinyl aromatic compound may be copolymerized. Examples of such alpha-olefins include alpha-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene. Among them, preferred is propylene, 1-butene, 1-pentene, 1-hexene or 1-octene. These alpha-olefins may be used alone or in combination of two or more.
In the ethylene/alpha-olefin/aromatic vinyl compound random copolymer, the amount of the constituent unit derived from ethylene is 60 to 90 mol%, the amount of the constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms is not more than 39 mol%, and the amount of the constituent unit derived from an aromatic vinyl compound is 1 to 40 mol%, provided that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%. It is preferable that the amount of the constitutional unit derived from ethylene is 65 to 85 mol%, the amount of the constitutional unit derived from an α -olefin having 3 to 20 carbon atoms is 10 to 32 mol%, and the amount of the constitutional unit derived from an aromatic vinyl compound is 5 to 25 mol%, provided that the total amount of the constitutional unit derived from ethylene and the constitutional unit derived from an α -olefin is 75 to 95 mol%.
When the amount of the constituent unit derived from ethylene, the amount of the constituent unit derived from an α -olefin having 3 to 20 carbon atoms and the amount of the constituent unit derived from an aromatic vinyl compound are within the above-mentioned ranges, the α -olefin/aromatic vinyl compound random copolymer has excellent lubricating properties such as an effect of improving low-temperature fluidity.
Among such copolymers as described above, preferred is an α -olefin/aromatic vinyl compound random copolymer in which the total amount of constituent units derived from an α -olefin having 3 to 20 carbon atoms and constituent units derived from an aromatic vinyl compound is 6 to 39 mol%, preferably 13 to 32 mol%, more preferably 15 to 30 mol%.
The α -olefin/aromatic vinyl compound random copolymer may be copolymerized with other monomers such as a non-conjugated diene. Examples of the non-conjugated diene are the same as those described above.
The alpha-olefin/aromatic vinyl compound random copolymer has an intrinsic viscosity [ eta ] of 0.01 to 1.0dl/g, preferably 0.05 to 0.5dl/g, as measured in decalin at 135 ℃.
The content of the α -olefin/aromatic vinyl compound random copolymer which functions as a fuel oil fluidity improver in the fuel oil composition is from 0.005 to 5.0% by weight, preferably from 0.01 to 1.0% by weight.
Alpha-olefin/aromatic vinyl Compound random copolymer used in the present inventionIn (3), it is desirable that the ratio of the constituent unit forming the two constituent unit sequences derived from the aromatic vinyl compound to all the constituent units derived from the aromatic vinyl compound is not more than 1%, preferably not more than 0.1%. The ratio of the two sequences of constituent units from the aromatic vinyl compound may be determined by13C-NMR measurement.
The α -olefin/aromatic vinyl compound random copolymer can be produced by the above-mentioned method for producing an α -olefin/aromatic vinyl compound random copolymer.
Effects of the invention
The lubricating oil and the first lubricating oil composition of the present invention have excellent compatibility with lubricating oil additives and have excellent viscosity properties, thermal stability, oxidation stability and wear resistance.
The second lubricating oil composition of the present invention has excellent lubricating oil properties because it comprises a base oil composed of a mineral oil and/or a hydrocarbon synthetic oil and a viscosity index improver or a base oil each containing a specific α -olefin/aromatic vinyl compound random copolymer.
The third lubricating oil composition of the present invention has excellent lubricating oil properties because it comprises a base oil composed of a mineral oil and/or a hydrocarbon synthetic oil, a compatibility improver or base oil each containing a specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer, a lubricating oil additive and optionally a viscosity index improver containing a specific α -olefin/aromatic vinyl compound random copolymer.
The present invention also provides a viscosity index improver comprising a specific α -olefin/aromatic vinyl compound random copolymer, and a lubricating oil compatibility improver comprising a specific low-molecular-weight α -olefin/aromatic vinyl compound random copolymer.
The alpha-olefin/aromatic vinyl type fuel oil fluidity improver constituting the fuel oil composition of the present invention can prevent the formation of wax crystals in the middle distillate fuel oil, thereby preventing the viscosity of the middle distillate fuel oil from increasing and lowering the Cold Filter Plugging Point (CFPP) and pour point. Also, the fluidity improver has excellent lubricating properties. Due to these excellent properties, the fuel supply and the air supply can be stabilized for the purpose of safe operation, and the wear of the fuel nozzle can be suppressed.
Therefore, the fuel oil composition of the present invention can prevent the viscosity of middle distillate fuel oil from increasing and reduce the cold filter plugging point and pour point. In addition, the fuel oil composition helps to inhibit wear of the fuel nozzle.
Examples
The invention will be further described with reference to the following examples, but it should be understood that the invention is not limited to these examples.
Example A-1
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
A1 liter glass reactor equipped with a cooling tube and a stirrer was thoroughly purged with nitrogen. 425ml of toluene and 75ml of styrene were charged into the reactor. The reactor was then saturated with ethylene with stirring. The temperature of the system was raised to 40 ℃ and 30.0mM methylaluminoxane (TOHSOAQUZO Co., 10 wt% in toluene) and 0.06mM (t-butylamino) dimethyl (tetramethyl-. eta.) were added to the system5Cyclopentadienyl) silane titanium dichloride (0.01mM in toluene) so that the molar ratio of Al to catalyst is 500. Then, ethylene was continuously fed at a rate of 100Nl/hr, and polymerization was carried out at 80 ℃ for 60 minutes.
After completion of the polymerization, 250ml of isobutanol and 10ml of hydrochloric acid were added, and the mixture was stirred at 80 ℃ for 30 minutes. The reaction solution containing isobutanol was transferred to a separatory funnel, washed twice with 250ml of water, and separated into an oil phase and an aqueous phase. The oil phase portion was added to 3 liters of methanol to precipitate a polymer. The precipitated polymer was vacuum-dried at 130 ℃ for 12 hours to obtain 20g of an ethylene/styrene random copolymer.
In the copolymer (a), the molar ratio of ethylene to styrene (ethylene/styrene) was 69/31. The copolymer (a) had an intrinsic viscosity (. eta.) of 0.3dl/g as measured in decalin at 135 ℃.
The viscosity of the copolymer, its total acid number and its properties after the heat resistance test are shown in Table 1.
The copolymers are useful as synthetic lubricating oils. As a result, the polymer showed good properties.
Example A-2
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
An ethylene/propylene/styrene random copolymer was synthesized in the same manner as in example A-1, except that 450ml of toluene and 50ml of styrene were charged into the reactor, and ethylene and propylene were continuously fed at rates of 95Nl/hr and 5Nl/hr, respectively.
The molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) in the copolymer was 69/11/20. The copolymer (b) had an intrinsic viscosity (. eta.) of 0.4dl/g as measured in decalin at 135 ℃.
The viscosity of the copolymer, its total acid number and its properties after the heat resistance test are shown in Table 1.
The copolymers are useful as synthetic lubricating oils. As a result, the polymer showed good properties.
Examples A to 3
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
An ethylene/propylene/styrene random copolymer was synthesized in the same manner as in example A-1, except that 450ml of toluene and 50ml of styrene were charged into the reactor, and ethylene and propylene were continuously fed at rates of 85Nl/hr and 15Nl/hr, respectively.
The molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) in the copolymer was 62/19/19. The copolymer (c) had an intrinsic viscosity (. eta.) of 0.4dl/g as measured in decalin at 135 ℃.
The viscosity of the copolymer, its total acid number and its properties after the heat resistance test are shown in Table 1.
The copolymers are useful as synthetic lubricating oils. As a result, the polymer showed good properties.
Examples A to 4
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
A1 liter glass reactor equipped with a cooling tube and a stirrer was thoroughly purged with nitrogen. 425ml of toluene and 75ml of styrene were charged into the reactor. The reactor was then saturated with ethylene with stirring. The temperature of the system was raised to 40 ℃ and 30.0mM methylaluminoxane (TOHSOAQUZO Co., 10 wt% in toluene) and 0.06mM [ (C)5Me4)SiMe2(N-t-Bu)〕TiCl2((tert-butylamino) dimethyl (tetramethyl-. eta.))5Cyclopentadienyl) silane titanium dichloride) (0.01mM in toluene) to give a molar ratio of Al to catalyst of 500. Then, ethylene, propylene and hydrogen were continuously fed at rates of 85Nl/hr, 15Nl/hr and 2Nl/hr, respectively, and polymerization was carried out at 80 ℃ for 60 minutes. After completion of the polymerization, 250ml of isobutanol and 10ml of hydrochloric acid were added, and the mixture was stirred at 80 ℃ for 30 minutes. The reaction solution containing isobutanol was transferred to a separatory funnel, washed twice with 250ml of water, and separated into an oil phase and an aqueous phase. The oil phase portion was added to 3 liters of methanol to precipitate a polymer. The precipitated polymer was vacuum-dried at 130 ℃ for 12 hours to obtain an ethylene/propylene/styrene random copolymer.
In this copolymer, the molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) was 68/29/3. The copolymer (d) had an intrinsic viscosity (. eta.) of 0.1dl/g as measured in decalin at 135 ℃.
The viscosity of the copolymer, its total acid number and its properties after the heat resistance test are shown in Table 1.
The copolymers are useful as synthetic lubricating oils. As a result, the polymer showed good properties.
Examples A to 5
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
A1 liter glass reactor equipped with a cooling tube and a stirrer was thoroughly purged with nitrogen. 425ml of toluene and 75ml of styrene were charged into the reactor. The reactor was then saturated with ethylene with stirring. The temperature of the system was raised to 80 ℃ and 30.0mM methylaluminoxane (TOHSOAQUZO Co., 10 wt% in toluene) and 0.06mM [ (C)5Me4)SiMe2(N-t-Bu)〕TiCl2((tert-butylamino) dimethyl (tetramethyl-. eta.))5Cyclopentadienyl) silane titanium dichloride) (0.01mM in toluene) to give a molar ratio of Al to catalyst of 500. Then, ethylene, propylene and hydrogen were continuously fed at rates of 51Nl/hr, 9Nl/hr and 40Nl/hr, respectively, and polymerization was carried out at 80 ℃ for 60 minutes.
After completion of the polymerization, 250ml of isobutanol and 10ml of hydrochloric acid were added, and the mixture was stirred at 80 ℃ for 30 minutes. The reaction solution containing isobutanol was transferred to a separatory funnel, washed twice with 250ml of water, and separated into an oil phase and an aqueous phase. The oil phase portion was added to 3 liters of methanol to precipitate a polymer. The precipitated polymer was vacuum-dried at 130 ℃ for 12 hours to obtain an ethylene/propylene/styrene random copolymer.
In this copolymer, the molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) was 69/28/3. The copolymer (e) had an intrinsic viscosity (. eta.) of 0.03dl/g as measured in decalin at 135 ℃.
The viscosity of the copolymer, its total acid number and its properties after the heat resistance test are shown in Table 1.
The copolymers are useful as synthetic lubricating oils. As a result, the polymer showed good properties.
Examples A to 6
Except that isopropylidenediindenyl zirconium dichloride is used instead of (tert-butylamino) dimethyl (tetramethyl-. eta.) (5An ethylene/propylene/styrene random copolymer was synthesized in the same manner as in example A-5 except for-cyclopentadienyl) silane titanium dichloride.
In this copolymer, the molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) was 72/25/3. The copolymer (f) had an intrinsic viscosity (. eta.) of 0.01dl/g as measured in decalin at 135 ℃.
The viscosity of the copolymer, its total acid number and its properties after the heat resistance test are shown in Table 1.
The copolymers are useful as synthetic lubricating oils. As a result, the polymer showed good properties.
Examples A to 7
95.0 parts by weight of the ethylene/propylene/styrene random copolymer (e) obtained in example A-5 was mixed with 5.0 parts by weight of a load-resistant additive at about 60 ℃ to prepare a mixed oil.
The kinematic viscosity and appearance (compatibility with the load-resistant additives) of the blended oils are set forth in Table 2.
Comparative example A-1
A mixed oil was prepared in the same manner as in example A-7 except that PAO-40 (1-decene oligomer, available from Mobil Co., Ltd.; trade name: SHF-401) was used in place of the ethylene/propylene/styrene random copolymer (e) obtained in example A-5.
The kinematic viscosity and appearance (compatibility with the load-resistant additives) of the blended oils are set forth in Table 2.
Comparative example A-2
A blend oil was prepared by blending 90.0 parts by weight of PAO-40 (1-decene oligomer), 5.0 parts by weight of an ester (DIDA: diisodecyl adipate, available from Daihachi Kagaku Kogyosho) and 5.0 parts by weight of a load-resistant additive at about 60 ℃.
The kinematic viscosity and appearance (compatibility with the load-resistant additives) of the blended oils are set forth in Table 2.
TABLE 1
| Examples | ||||||
| A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | |
| Intrinsic viscosity (. eta.) (dl/g) viscosity at 100 ℃*1 (mPa. multidot.S) Total acid number*2(mg-KOH/g) | 0.316,5000.18 | 0.449,0000.11 | 0.454,0000.13 | 0.11500.05 | 0.03390.04 | 0.019.50.02 |
| Lubrication Property four-ball load resistance test*3(kg/cm2) | - | - | - | 4.0 | 3.0 | 2.5 |
| Heat resistance test*Loss of Property by Evaporation after 4(200 ℃ C.. times.6.5 hours)*5 (wt%) total acid number*6(mg-KOH/g) | 0.83.80 | 0.54.30 | 0.54.10 | 3.04.50 | 13.04.00 | 20.54.05 |
Note:
*1: measured by a Brookfield viscometer (DV-II).
*2: measured by the method prescribed in JIS K2501.
*3: measured by a method prescribed in JIS K2519.
*4: the heat resistance test was measured by the original method of my company by heating a 30g sample contained in a cylindrical glass container (diameter: 55mm, height: 35mm) in an oven at 200 ℃ for 6.5 hours.
*5: test for measuring Heat resistance (*4) Followed by weight loss.
*6: in the Heat resistance test (*4) Thereafter, the measurement was carried out by the method prescribed in JIS K2501.
TABLE 2
| Examples | Comparative example | ||
| A-7 | A-1 | A-2 | |
| Component proportions (wt%) of Mixed oils the copolymer PAO-40 ester (DIDA) Charge-resistant additive of example A-5 | 95.05.0 | 95.05.0 | 90.05.05.0 |
| In total (wt%) | 100.0 | 100.0 | 100.0 |
| Properties of the Mixed oil kinematic viscosity at 100 ℃*1(mm2S) appearance*2 (compatibility with additives) | 37.5 good | 36.5 difference | 34.0 is good |
Note:
*1: measured by the method prescribed in JIS K2283.
*2: evaluation was by visual observation.
Example B-1
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
A1 liter glass reactor equipped with a cooling tube and a stirrer was thoroughly purged with nitrogen. 425ml of toluene and 75ml of styrene were charged into the reactor. The reactor was then saturated with ethylene with stirring. Temperature of the systemTo the system were added 30.0mM methylaluminoxane (TOHSOAQUZO Co., 10 wt% in toluene) and 0.06mM (t-butylamino) dimethyl (tetramethyl-. eta.)5Cyclopentadienyl) silane titanium dichloride (0.01mM in toluene) so that the molar ratio of Al to catalyst is 500. Then, ethylene was continuously fed at a rate of 100Nl/hr, and polymerization was carried out at 80 ℃ for 60 minutes.
After completion of the polymerization, 250ml of isobutanol and 10ml of hydrochloric acid were added, and the mixture was stirred at 80 ℃ for 30 minutes. The reaction solution containing isobutanol was transferred to a separatory funnel, washed twice with 250ml of water, and separated into an oil phase and an aqueous phase. The oil phase portion was added to 3 liters of methanol to precipitate a polymer. The precipitated polymer was vacuum-dried at 130 ℃ for 12 hours to obtain 24g of an ethylene/styrene random copolymer.
In this copolymer, the molar ratio of ethylene to styrene (ethylene/styrene) was 71/29. The copolymer (g) had an intrinsic viscosity (. eta.) of 1.1dl/g as measured in decalin at 135 ℃.
Preparation of lubricating oil compositions
The copolymer (g) was dissolved in mineral oil a (available from Fuji Kosansha, 100 neutral oil) at a concentration of 10% by weight of mineral oil a under heating to prepare a viscous liquid. The viscous liquid was mixed with mineral oil B (a 150 neutral oil available from Fuji Kosansha) to give a mixed oil having a viscosity of about 11mm at 100 deg.C2and/S. The kinematic viscosity, viscosity index and oxidation stability of the resulting mixed oil were measured. The results are shown in Table 3.
Example B-2
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
An ethylene/propylene/styrene random copolymer was synthesized in the same manner as in example B-1, except that 450ml of toluene and 50ml of styrene were charged into the reactor, and ethylene and propylene were continuously fed at rates of 95Nl/hr and 5Nl/hr, respectively.
The molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) in the copolymer was 71/10/19. The copolymer (h) had an intrinsic viscosity (. eta.) of 1.5dl/g as measured in decalin at 135 ℃.
Preparation of lubricating oil compositions
A mixed oil was prepared in the same manner as in example B-1, except that the copolymer (h) was used.
The kinematic viscosity, viscosity index and oxidation stability of the mixed oils are shown in Table 3.
Example B-3
Synthesis of alpha-olefin/aromatic vinyl Compound random copolymer
An ethylene/propylene/styrene random copolymer was synthesized in the same manner as in example B-1, except that 450ml of toluene and 50ml of styrene were charged into the reactor, and ethylene and propylene were continuously fed at rates of 85Nl/hr and 15Nl/hr, respectively.
The molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) in the copolymer was 59/21/20. The copolymer (i) had an intrinsic viscosity (. eta.) of 1.6dl/g as measured in decalin at 135 ℃.
Preparation of lubricating oil compositions
A mixed oil was prepared in the same manner as in example B-1, except that the copolymer (i) was used.
The kinematic viscosity, viscosity index and oxidation stability of the mixed oils are shown in Table 3.
Example B-4
A mixed oil was prepared in the same manner as in example B-1, except that a viscous liquid composed of the ethylene/styrene random copolymer (g) and mineral oil A (available from Fuji Kosansha, 100 neutral oil) was mixed with low-viscosity PAO-6 (1-decene oligomer available from Shinnittetsu Kagaku K.K., trade name: Shinfluid 61) in place of mineral oil B, and the resultant mixed oil was allowed to have a viscosity of about 11mm at 100 ℃2and/S. Measuring kinematic viscosity and viscosity of the obtained mixed oilDegree index and oxidation stability. The results are shown in Table 3.
Example B-5
A viscous liquid was prepared in the same manner as in example B-1, except that the ethylene/styrene random copolymer (g) was dissolved under heating in a low-viscosity PAO-4 (1-decene oligomer available from Shinnittetsu Kagaku K.K., trade name: Shinfluid 41) in a concentration of 10% by weight based on the PAO-4 in place of the mineral oil A. Then, similarly to example B-4, a viscous liquid was mixed with a low-viscosity PAO-6 (1-decene oligomer available from Shinnittetsu Kagaku K.K., trade name: Shinfluid 61) to give a mixed oil having a viscosity of about 11mm at 100 ℃2and/S. The kinematic viscosity, viscosity index and oxidation stability of the resulting mixed oil were measured. The results are shown in Table 3.
Example B-6
A viscous liquid obtained in example B-1 of a mixture of an ethylene/styrene random copolymer (g) and a mineral oil A was mixed with a detergent dispersant as a compatibility improver, a low molecular weight α -olefin/aromatic vinyl compound random copolymer (ethylene/propylene/styrene random copolymer, ethylene/propylene/styrene molar ratio: 69/11/20, intrinsic viscosity [ η ] measured in decalin at 135 ℃ C.: 0.2dl/g) and a base oil PAO-6 (1-decene oligomer available from Shinnittetsu Kagaku K.K., trade name: Shinfluid 61) to prepare a mixed oil.
The kinematic viscosity, viscosity index and appearance (compatibility with additives) of the blended oils are listed in Table 4.
Comparative example B-1
A mixed oil was prepared in the same manner as in example B-6, except that an ester (DIDA: diisodecyl adipate, available from Daihachi Kagaku Kogyosho) was used as a compatibility improver in place of the low-molecular weight α -olefin/aromatic vinyl compound random copolymer.
The kinematic viscosity, viscosity index and appearance (compatibility with additives) of the blended oils are listed in Table 4.
Comparative example B-2
A mixed oil was prepared in the same manner as in example B-6, except that a low-molecular-weight α -olefin/aromatic vinyl compound random copolymer was not used as the compatibility improver.
The kinematic viscosity, viscosity index and appearance (compatibility with additives) of the blended oils are listed in Table 4.
TABLE 3
| Examples | |||||
| B-1 | B-2 | B-3 | B-4 | B-5 | |
| Composition ratio of viscous liquid (wt%) copolymer of example B-1 copolymer of example B-2 copolymer of example B-3 copolymer mineral oil A (100 neutral) PAO-4 | 10.090.0 | 10.090.0 | 10.090.0 | 10.090.0 | 10.090.0 |
| In total (wt%) | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Component ratio (wt%) of the Mixed oil viscous liquid mineral oil BPAO-6 | 24.076.0 | 18.581.5 | 15.584.5 | 25.374.7 | 25.874.2 |
| In total (wt%) | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Intrinsic kinematic viscosity of the Mixed oils*1(mm2S) viscosity index at 100 ℃ 40 ℃*2 Properties after Oxidation test*Ratio of kinematic viscosity*4(40 ℃ C.) Total acid number*5(mg-KOH/g) | 11.1068.81530.665.6 | 10.9967.51540.685.1 | 11.0468.11530.655.0 | 11.0261.91720.754.0 | 10.9660.31760.733.8 |
Note:
*1: measured according to the method prescribed in JIS K2283.
*2: calculated according to the method prescribed in JIS K2283.
*3: evaluated according to the method prescribed in JIS K2514 (165.5 ℃ C. times.48 hours).
*4: the kinematic viscosity at 40 ℃ after the oxidation test/the kinematic viscosity at 40 ℃ before the oxidation test were measured according to the method specified in JIS K2283.
*5: measured according to the method prescribed in JIS K2501.
TABLE 4
| Examples | Comparative example | ||
| B-6 | B-1 | B-2 | |
| Component proportion (wt%) of the mixed oil | |||
| (1) Viscous liquid (mixture of copolymer of example B-1 and mineral oil A) | 14.0 | 14.0 | 14.0 |
| (2) Detergent-dispersant (SH grade) | 10.5 | 10.5 | 10.5 |
| (3) Compatibility improver (i) Low molecular weight alpha-olefin/aromatic vinyl Compound random copolymer (ii) ester (DIDA) | 5.0 | 5.0 | |
| (4) Base oil (PAO-6) | 70.5 | 70.5 | 75.5 |
| In total (wt%) | 100.0 | 100.0 | 100.0 |
| Properties of the Mixed oil | |||
| Kinematic viscosity*1(mm2/S) | |||
| 100℃ | 12.4 | 10.2 | 10.8 |
| 40℃ | 72.2 | 56.1 | 62.1 |
| Viscosity index*2 | 170 | 172 | 166 |
| Appearance (compatibility with additives) | Good effect | Good effect | Difference (D) |
Note:
*1: measured according to the method prescribed in JIS K2283.
*2: calculated according to the method prescribed in JIS K2283.
*3: the evaluation was visually observed.
Example C-1
(1) Synthesis of ethylene/styrene random copolymer (A)
A1 liter glass reactor equipped with a cooling tube and a stirrer was thoroughly purged with nitrogen. 450ml of toluene and 50ml of styrene were charged into the reactor. The reactor was then saturated with ethylene with stirring. The temperature of the system was raised to 40 ℃ and 30.0mM methylaluminoxane (TOHSOAQUZO Co., 10 wt% in toluene) and 0.06mM [ (C5 Me)4)SiMe2(N-t-Bu)〕TiCl2((tert-butylamino) dimethyl (tetramethyl-. eta.))5Cyclopentadienyl) silane titanium dichloride) (0.01mM in toluene) to give a molar ratio of Al to catalyst of 500. Then, ethylene was continuously fed at a rate of 100NL/hr, and polymerization was carried out at 80 ℃ for 60 minutes. After completion of the polymerization, 250ml of isobutanol and 10ml of hydrochloric acid were added, and the mixture was stirred at 80 ℃ for 30 minutes. The reaction solution containing isobutanol was transferred to a separatory funnel, washed twice with 250ml of water, and separated into an oil phase and an aqueous phase. The oil phase portion was added to 3 liters of methanol to precipitate a polymer. Precipitated polymersVacuum drying at 130 ℃ for 12 hours gave an ethylene/styrene random copolymer (A).
In the copolymer (A), the molar ratio of ethylene to styrene (ethylene/styrene) was 81/19. The copolymer (A) had an intrinsic viscosity (. eta.) of 0.4dl/g as measured in decalin at 135 ℃.
(2) Evaluation of Properties of Fuel composition
To a commercially available No. 2 gas oil (sulfur content: 0.1% by weight) was added 0.02% by weight of an ethylene/styrene random copolymer (A). The resulting compositions were evaluated for pour point, Cold Filter Plugging Point (CFPP) and lubricating properties.
The results are shown in Table 5.
Example C-2
A fuel oil composition was prepared in the same manner as in example C-1 except that the content of the ethylene/styrene random copolymer (A) in the fuel oil composition was changed to 0.10% by weight. The composition was evaluated in the same manner as in example C-1.
The results are shown in Table 5.
Example C-3
(1) Synthesis of ethylene/propylene/styrene random copolymer (B)
An ethylene/propylene/styrene random copolymer (B) was produced in the same manner as in example C-1, except that 4,750ml of toluene and 25ml of styrene were charged into the reactor, and ethylene and propylene were continuously fed at rates of 100NL/hr and 5NL/hr, respectively.
In the ethylene/propylene/styrene random copolymer (B), the molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) was 78/11/11. The copolymer (B) had an intrinsic viscosity (. eta.) of 0.3dl/g as measured in decalin at 135 ℃.
(2) Evaluation of Properties of Fuel composition
A fuel oil composition was evaluated in the same manner as in example C-1, except that the ethylene/propylene/styrene random copolymer (B) was used.
The results are shown in Table 5.
Example C-4
A fuel oil composition was prepared in the same manner as in example C-3 except that the content of the ethylene/propylene/styrene random copolymer (B) in the fuel oil composition was changed to 0.10% by weight. The composition was evaluated in the same manner as in example C-3.
The results are shown in Table 5.
Example C-5
(1) Synthesis of ethylene/propylene/styrene random copolymer (C)
An ethylene/propylene/styrene random copolymer (C) was produced in the same manner as in example C-1, except that 4,880ml of toluene and 12ml of styrene were charged into the reactor, and ethylene and propylene were continuously fed at rates of 95NL/hr and 6NL/hr, respectively.
In the ethylene/propylene/styrene random copolymer (C), the molar ratio of ethylene, propylene and styrene (ethylene/propylene/styrene) was 79/16/5. The copolymer (C) had an intrinsic viscosity (. eta.) of 0.4dl/g as measured in decalin at 135 ℃.
(2) Evaluation of Properties of Fuel composition
A fuel oil composition was evaluated in the same manner as in example C-1, except that the ethylene/propylene/styrene random copolymer (C) was used.
The results are shown in Table 5.
Comparative example C-1
The pour point, cold filter clogging point and lubricating properties of the commercial No. 2 gas oil used in example C-1 were evaluated.
The results are shown in Table 5.
Example C-6
A fuel oil composition was prepared in the same manner as in example C-3 except that a low-sulfur gas oil (sulfur content: not more than 0.01% by weight) was used in place of the gas oil. The composition was evaluated in the same manner as in example C-3.
The results are shown in Table 6.
Example C-7
A fuel oil composition was prepared in the same manner as in example C-6 except that the content of the ethylene/propylene/styrene random copolymer in the fuel oil composition was changed to 0.10% by weight. The composition was evaluated in the same manner as in example C-6.
The results are shown in Table 6.
Comparative example C-2
The same gas oil (sulfur content: not more than 0.01% by weight) as used in example C-7 was evaluated in the same manner as described above.
The results are shown in Table 6.
TABLE 5
| Examples | Comparative example | |||||
| C-1 | C-2 | C-3 | C-4 | C-5 | C-1 | |
| Component proportion (wt%) of alpha-olefin/aromatic vinyl compound random copolymer gas oil (sulfur content: 0.1 wt%) | 0.0299.98 | 0.1099.90 | 0.0299.98 | 0.1099.90 | 0.0299.98 | --100.0 |
| In total (wt%) | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Properties pour Point (. degree. C.) Cold Filter plugging Point (. degree. C.) lubricating Properties (coefficient of friction) of Fuel oil compositions | -22.5-70.238 | -25.0-80.226 | -25.0-70.234 | -30.0-90.222 | -25.0-80.225 | -15.0-30.260 |
TABLE 6
| Examples | Comparative example | ||
| C-6 | C-7 | C-2 | |
| Component proportion (wt%) of alpha-olefin/aromatic vinyl compound random copolymer low-sulfur gas oil (sulfur content: not more than 0.01 wt%) | 0.0299.98 | 0.1099.90 | --100.0 |
| In total (wt%) | 100.0 | 100.0 | 100.0 |
| Properties pour Point (. degree. C.) Cold Filter plugging Point (. degree. C.) lubricating Properties (coefficient of friction) of Fuel oil compositions | -25.0-80.246 | -30.0-90.234 | -17.5-40.272 |
The evaluation method comprises the following steps:
the pour point was measured according to the method of JIS K2269.
The clogging point of the cold filter was measured in accordance with JIS K2288.
The lubricating properties were evaluated in terms of the coefficient of friction measured using an SRV friction tester (from Optimol Co.) under conditions of a test initiation temperature of 60 ℃, sample contact with steel ball/plate, load of 20N, frequency of 50Hz, and amplitude of 1mm for 30 minutes.
Claims (3)
1. A lubricating oil comprising an α -olefin/aromatic vinyl compound random copolymer, said copolymer comprising:
40 to 75 mol% of constituent units derived from ethylene,
0 to 45 mol% of a constituent unit derived from an alpha-olefin having 3 to 20 carbon atoms, and
1 to 40 mol% of a constituent unit derived from an aromatic vinyl compound,
provided that the total amount of the constituent unit derived from ethylene and the constituent unit derived from an alpha-olefin is 60 to 99 mol%,
the alpha-olefin/aromatic vinyl compound random copolymer has an intrinsic viscosity [ eta ] of 0.01 to 0.50dl/g as measured in decalin at 135 ℃.
2. The lubricant oil of claim 1, further comprising a lubricant additive.
3. The lubricating oil composition according to claim 2, wherein the lubricating oil additive is at least one additive selected from the group consisting of an extreme pressure additive, an anti-wear agent, an oiliness improver and a detergent dispersant.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1950797 | 1997-01-31 | ||
| JP1950697 | 1997-01-31 | ||
| JP19507/97 | 1997-01-31 | ||
| JP19506/97 | 1997-01-31 | ||
| JP2763197 | 1997-02-12 | ||
| JP27631/97 | 1997-02-12 | ||
| PCT/JP1998/000212 WO1998033872A1 (en) | 1997-01-31 | 1998-01-21 | Lubricating oil or lubricating oil composition and fuel oil composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1019891A1 HK1019891A1 (en) | 2000-03-03 |
| HK1019891B true HK1019891B (en) | 2003-05-23 |
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