Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
• • 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
  • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
  • C10M101/02—Petroleum fractions
• • 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
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/17—Fisher Tropsch reaction products
  • C10M2205/173—Fisher Tropsch reaction products used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/68—Shear stability
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/70—Soluble oils

Definitions

• the present invention relates to viscosity index improver compositions and lubricating oil compositions.
• grade 0W-20 oil as having a high temperature high shear (HTHS) viscosity at 150°C (ASTM D4683 or D5481) of 2.6 mPa ⁇ s or higher and grade 0W-16 oil as having an HTHS viscosity at 150°C of 2.3 mPa ⁇ s or higher.
• HTHS high temperature high shear
• hybrid vehicles and plug-in hybrid vehicles which use both electricity and gasoline, and other hardware approaches are also being developed to lower fuel consumption.
• such hybrid vehicles have low engine oil temperatures during driving.
• the engine oil temperature during normal driving is usually 80°C to 100°C in gasoline-driven vehicles, while it is 40°C to 80°C in hybrid vehicles.
• engine oils used in hybrid or similar vehicles require even lower viscosity in the range of 40°C to 80°C.
• Viscosity index improvers that have been used include methacrylate copolymers (Patent Literatures 1 to 3) and comb copolymers (Patent Literatures 4 to 6).
• Comb copolymers are particularly known to have high modifying effect on the temperature dependence of the viscosity.
• viscosity index improvers are generally distributed in the form of viscosity index improver compositions containing high concentrations of copolymers in base oils.
• viscosity index improver compositions containing high concentrations of comb copolymers may form gels when exposed to high-temperature environments in summer or to low-temperature environments in winter or in cold regions.
• the present invention aims to provide a viscosity index improver composition that is less likely to form gels.
• R 1 is a hydrogen atom or a methyl group
• -X 1 - is a group represented by -O-, -O(AO) m -, or - NH-
• A is a C2-C4 alkylene group
• m is an integer of 1 to 10, and each A may be the same or different when m is 2 or greater
• R 2 is a residue after removal of one hydrogen atom from a hydrocarbon polymer containing a 1,2-butylene group as a structural unit
• p represents a number of 0 or 1.
• the viscosity index improver composition of the present invention is advantageously less likely to form gels.
• the viscosity index improver composition of the present invention contains a copolymer (A) containing, as essential constituent monomers, a polyolefin-based monomer (a) represented by the following formula (1) and an alkyl (meth)acrylate (b) having a C1-C4 alkyl group, and a Fischer-Tropsch derived base oil (B) having a kinematic viscosity at 100°C of 4.0 mm 2 /s or less, the copolymer (A) containing the monomer (a) in an amount of 1 to 20 wt% and the alkyl (meth)acrylate (b) in an amount of 45 to 85 wt% based on the total weight of the monomers constituting the copolymer (A).
• A a copolymer containing, as essential constituent monomers, a polyolefin-based monomer (a) represented by the following formula (1) and an alkyl (meth)acrylate (b) having a C1-C4 al
• the copolymer (A) in the present invention contains, as essential constituent monomers, a polyolefin-based monomer (a) represented by the formula (1) and an alkyl (meth)acrylate (b) having a C1-C4 alkyl group.
• the polyolefin-based monomer (a) in the present invention is a monomer obtained by modifying the later-described hydrocarbon polymer and reacting the modified hydrocarbon polymer with (meth)acrylic acid.
• (meth)acrylic means methacrylic or acrylic.
• R 1 in the formula (1) is a hydrogen atom or a methyl group. Of these, a methyl group is preferred in terms of viscosity index improving effect.
• Examples of the C2-C4 alkylene group include an ethylene group, a 1,2- or 1,3-propylene group, and a 1,2-, 1,3-, or 1,4-butylene group.
• n is an integer of 1 to 10, and it is preferably an integer of 1 to 4, more preferably an integer of 1 to 2 in terms of HTHS viscosity in the effective temperature range (80°C to 150°C).
• -X 1 - is preferably a group represented by -O- or -O(AO) m -, more preferably a group represented by -O- or -O(CH 2 CH 2 O)-.
• p represents a number of 0 or 1.
• R 2 in the formula (1) is a residue after removal of one hydrogen atom from a hydrocarbon polymer containing a 1,2-butylene group (-CH 2 CH(CH 2 CH 3 )- or CH(CH 2 CH 3 )CH 2 -) as a structural unit.
• hydrocarbon polymer containing a 1,2-butylene group as a structural unit examples include a polymer containing 1-butene as a constituent monomer and a polymer obtained by hydrogenating a terminal carbon-carbon double bond of a poly(1,3-butadiene), which is a product of 1,2-addition of 1,3-butadiene.
• the monomer (a) can be obtained by esterification of a polymer (Y) having a hydroxy group at one end with (meth)acrylic acid.
• the polymer (Y) can be obtained by introducing a hydroxy group to one end of a hydrocarbon polymer.
• the monomer (a) can be obtained by transesterification of a polymer (Y) having a hydroxy group at one end with an alkyl (preferably C1-C4 alkyl) (meth)acrylate such as methyl (meth)acrylate.
• polymer (Y) having a hydroxy group at one end include the following (Y1) to (Y4).
• Maleic anhydride-ene-amino alcohol adduct examples include a product obtained by amino alcohol-mediated imidization of a reaction product obtained by an ene reaction of a hydrocarbon polymer of an unsaturated hydrocarbon (x) having a double bond at one end with maleic anhydride.
• the monomer (a) is a compound represented by the formula (1) in which -X 1 - is -O- and p is 1.
• Hydroformylated-hydrogenated product (Y4) examples include a product obtained by hydroformylation of a hydrocarbon polymer of an unsaturated hydrocarbon (x) having a double bond at one end, followed by hydrogenation (e.g., those disclosed in JP S63-175096 A ).
• the monomer (a) is a compound represented by the formula (1) in which -X 1 - is -O- and p is 0.
• alkylene oxide adducts Y1
• hydroborated products Y2
• alkylene oxide adducts Y1
• the proportion of butadiene of all monomers constituting R 2 in the formula (1) is preferably 50 wt% or more, more preferably 75 wt% or more, still more preferably 85 wt% or more, particularly preferably 90 wt% or more.
• the total amount of the isobutylene group and the 1,2-butylene group is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more based on the total number of moles of the constituent monomers of the hydrocarbon polymer.
• the following methods can be employed to increase the proportion of the total amount of the isobutylene group and the 1,2-butylene group in the hydrocarbon polymer.
• the proportion of the total amount of the isobutylene group and the 1,2-butylene group in the hydrocarbon polymer can be increased by, in anionic polymerization using 1,3-butadiene, setting the reaction temperature to be low ⁇ e.g., lower than or equal to the boiling temperature (-4.4°C) of 1,3-butadiene ⁇ and adding a polymerization initiator in an amount smaller than that of 1,3-butadiene.
• the proportion of the 1,2-butylene group can be measured by 13 C-NMR. Specifically, for example, when only C4 monomers are used, the proportion can be determined by analyzing the hydrocarbon polymer by 13 C-NMR and calculating the molar percentage of the 1,2-butylene group based on the total number of moles of the structural units of the hydrocarbon polymer by the following equation (1).
• 13 C-NMR a peak derived from the tertiary carbon atom (-CH 2 CH(CH 2 CH 3 )-) of the 1,2-butylene group appears at an integral value of 26 to 27 ppm (integral value B).
• the total proportion can be determined from the integral value of the peak and an integral value (integral value C) of all carbon peaks of the hydrocarbon polymer.
• Proportion of 1,2-butylene group (mol%) ⁇ (integral value B) ⁇ 4 ⁇ /(integral value C) ⁇ 100
• the proportion of the 1,2-butylene group can be adjusted as follows: for example, in the case of anionic polymerization using 1,3-butadiene, the proportion of the 1,2-butylene group can be increased by setting the reaction temperature to a temperature lower than or equal to the boiling point (-4.4°C) of 1,3-butadiene and adding a polymerization initiator in an amount smaller than that of 1,3-butadiene, whereas the proportion of the 1,2-butylene group can be decreased by setting the reaction temperature to a temperature higher than or equal to the boiling point of 1,3-butadiene and adding a polymerization initiator in an amount larger than that of 1,3-butadiene.
• the total amount of the isobutylene group and the 1,2-butylene group can be measured by 13 C-NMR.
• the proportion can be determined by analyzing the hydrocarbon polymer by 13 C-NMR and calculating the total molar percentage of the isobutylene group and the 1,2-butylene group based on the total number of moles of the structural units of the hydrocarbon polymer by the following equation (2).
• the hydrocarbon polymer in R 2 contains butadiene as a constituent monomer or butadiene and 1-butene as constituent monomers, in terms of viscosity index improving effect and copolymerizability with other monomers, the molar ratio of a 1,2-adduct to a 1,4-adduct (1,2-adduct/1,4-adduct) in a structure derived from butadiene or from butadiene and 1-butene constituting a part or the whole of R 2 in the formula (1) is preferably 5/95 to 95/5, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30.
• the SP tends to be smaller when R 2 has a higher degree of branching and a greater carbon number, while it tends to be greater when R 2 has a lower degree of branching and a smaller carbon number.
• the SP in the present invention means a value calculated by the Fedors method ( Polymer Engineering and Science, February 1974, vol. 14, No. 2, pp. 147 to 154 ) by substituting numerical values (heat of vaporization and molar volume of atoms or functional groups at 25°C) on page 152 (Table 5) into formula (28) on page 153 of the same journal.
• the SP can be calculated by substituting, into the equation below, the numerical values corresponding to the types of atoms and groups in the molecular structure among the numerical values of ⁇ e i and v i (Fedors' parameters) in Table 1 below.
• the SP of the structural unit derived from the monomer (a) can be calculated using the parameters described above based on the molecular structure of the structural unit derived from the monomer (a).
• the SP can be adjusted to a desired range by suitably adjusting the monomers (unsaturated hydrocarbons (x)) to be used and the weight fractions of the monomers.
• ethyl (meth)acrylate preferred among these are ethyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. More preferred are ethyl (meth)acrylate and n-butyl (meth)acrylate. Particularly preferred is n-butyl (meth)acrylate.
• the copolymer (A) may contain a (meth)acryloyl monomer (c) having a C9-C36 alkyl group and/or a monomer (d) represented by the following formula (2) as constituent monomer(s).
• R 4 in the formula (2) is a C2-C4 alkylene group.
• R 4 O is a C2-C4 alkyleneoxy group. Examples include an ethyleneoxy group, a 1,2- or 1,3-propyleneoxy group, and a 1,2-, 1,3-, or 1,4-butyleneoxy group.
• the monomer (d) include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate ⁇ e.g., 2-(n-butyloxy)ethyl (meth)acrylate, 2-(tert-butyloxy)ethyl (meth)acrylate, 2-(sec-butyloxy)ethyl (meth)acrylate, and 2-(isobutyloxy)ethyl (meth)acrylate ⁇ , phenoxyethyl (meth)acrylate, benzyl oxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, propoxypropyl (meth)acrylate, butoxypropyl (meth)acrylate ⁇ e.g., 2-(n-butyloxy)propyl (meth
• Preferred among the monomers (d) in terms of viscosity index improving effect and reduction of HTHS viscosity at 100°C are ethoxyethyl (meth)acrylate and butoxyethyl (meth)acrylate. More preferred is n-butoxyethyl (meth)acrylate.
• One or more of each of monomers (e) to (m) may be used.
• nitrogen atom-containing monomer (e) examples include the following monomers (e1) to (e4), excluding the monomers (a) to (d).
• Examples include (meth)acrylamides, N-(N'-monoalkylaminoalkyl) (meth)acrylamides (those having an aminoalkyl group (C2-C6) in which one C1-C4 alkyl group is bonded to a nitrogen atom, such as N-(N'-methylaminoethyl) (meth)acrylamide, N-(N'-ethylaminoethyl) (meth)acrylamide, N-(N'-isopropylamino-n-butyl) (meth)acrylamide, N-(N'-n-butylamino-n-butyl) (meth)acrylamide, and N-(N'-isobutylamino-n-butyl) (meth)acrylamide); dialkyl (meth)acrylamides (those in which two C1-C4 alkyl groups are bonded to a nitrogen atom, such as N,N-dimethyl (meth)acrylamide, N,
• Examples include 4-nitrostyrene.
• Examples include primary amino group-containing monomers ⁇ C3-C6 alkenylamines (e.g., (meth)allylamine and crotylamine) and aminoalkyl (C2-C6) (meth)acrylates (e.g., aminoethyl (meth)acrylate) ⁇ ; secondary amino group-containing monomers ⁇ monoalkylaminoalkyl (meth)acrylates (e.g., those having an aminoalkyl group (C2-C6) in which one C1-C6 alkyl group is bonded to a nitrogen atom, such as N-t-butylaminoethyl (meth)acrylate and N-methylaminoethyl (meth)acrylate), and C6-C12 dialkenylamines (e.g., di(meth)allylamine) ⁇ ; tertiary amino group-containing monomers ⁇ dialkylaminoalkyl (meth)acrylates (e.g., those having an aminoalkyl group
• Examples include (meth)acrylonitrile.
• the monomers (e) are the amide group-containing monomers (e1) and the primary to tertiary amino group-containing monomers (e3). More preferred are N-(N',N'-diphenylaminoethyl) (meth)acrylamide, N-(N',N'-dimethylaminoethyl) (meth)acrylamide, N-(N',N'-diethylaminoethyl) (meth)acrylamide, N-(N',N'-dimethylaminopropyl) (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate.
• Examples include hydroxy group-containing aromatic monomers (e.g., p-hydroxystyrene), hydroxyalkyl (C2-C6) (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate and 2- or 3-hydroxypropyl (meth)acrylate), mono- or bis-hydroxyalkyl (C1-C4) substituted (meth)acrylamides (e.g., N,N-bis(hydroxymethyl) (meth)acrylamide, N,N-bis(hydroxypropyl) (meth)acrylamide, and N,N-bis(2-hydroxybutyl) (meth)acrylamide), vinyl alcohol, C3-C12 alkenols (e.g., (meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol, and 1-undecenol), C4-C12 alkene monools or alkene diols (e.g., 1-buten-3-ol, 2-buten
• Examples also include mono(meth)acrylates of polyoxyalkylene glycols (carbon number of the alkylene group: C2-C4; polymerization degree: 2 to 50), polyoxyalkylene polyols (polyoxyalkylene ethers (carbon number of the alkylene group: C2-C4; polymerization degree: 2 to 100) of the tri- to octahydric alcohols), or alkyl (C1-C4) ethers of polyoxyalkylene glycols or polyoxyalkylene polyols (e.g., polyethylene glycol (Mn: 100 to 300) mono(meth)acrylate, polypropylene glycol (Mn: 130 to 500) mono(meth)acrylate, methoxy polyethylene glycol (Mn: 110 to 310) (meth)acrylate, lauryl alcohol ethylene oxide adduct (2 to 30 moles) (meth)acrylate, and polyoxyethylene (Mn: 150 to 230) sorbitan mono(meth)acrylate).
• Examples of the phosphorus atom-containing monomer (g) include the following monomers (g1) and (g2).
• Examples include styrene, ⁇ -methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, 4-crotylbenzene, indene, and 2-vinylnaphthalene.
• Preferred among the monomers (h) are styrene and ⁇ -methylstyrene. More preferred is styrene.
• Examples include divinylbenzene, C4-C12 alkadienes (e.g., butadiene, isoprene, 1,4-pentadiene, 1,6-heptadiene, and 1,7-octadiene), (di)cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, limonene, ethylene di(meth)acrylate, polyalkylene oxide glycol di(meth)acrylate, pentaerythritol triallyl ether, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and esters disclosed in WO 01/009242 such as an ester of an unsaturated carboxylic acid having a Mn of 500 or more and glycol and an ester of an unsaturated alcohol and a carboxylic acid.
• Vinyl esters, vinyl ethers, vinyl ketones (j) (sometimes abbreviated as the monomer (j)):
• Examples include vinyl esters of C2-C12 saturated fatty acids (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl octanoate), C1-C12 alkyl, aryl, or alkoxyalkyl vinyl ethers (e.g., methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl-2-methoxyethyl ether, and vinyl-2-butoxyethyl ether), and C1-C8 alkyl or aryl vinyl ketones (e.g., methyl vinyl ketone, ethyl vinyl ketone, and phenyl vinyl ketone).
• C2-C12 saturated fatty acids e.g., vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl octanoate
• C1-C12 alkyl aryl,
• Epoxy group-containing monomer (k) (sometimes abbreviated as the monomer (k)):
• Examples include glycidyl (meth)acrylate and glycidyl (meth)allyl ether.
• the weight percentage of the monomer (b) among the constituent monomers of the copolymer (A) is 45 to 85 wt%, preferably 50 to 85 wt%, more preferably 55 to 80 wt% based on the total weight of the monomers constituting the copolymer (A).
• a weight percentage of the monomer (b) of less than 45 wt% tends to lead to easy gelation of the viscosity index improver composition.
• a weight percentage of the monomer (b) of more than 85 wt% tends to lead to poor solubility of the copolymer (A) in base oil (Fischer-Tropsch derived base oil (B) and other base oils).
• the total weight percentage of the monomers (e) to (m) among the constituent monomers of the copolymer (A) is preferably 5 wt% or less, more preferably 1 wt% or less based on the total weight of the monomers constituting the copolymer (A).
• the copolymer (A) preferably has an Mw of 5,000 to 2,000,000. More preferred ranges vary depending on the application of the viscosity index improver composition and the lubricating oil composition containing the viscosity index improver composition. Table 2 shows the ranges.
• Conditions for measuring the Mw and molecular weight distribution (Mw/Mn) of the copolymer (A) are the same as the conditions for measuring the Mw and Mn of the monomer (a).
• the copolymer (A) preferably has a SP of 8.0 to 10.0 (cal/cm 3 ) 1/2 , more preferably 9.0 to 9.5 (cal/cm 3 ) 1/2 .
• the SP of the copolymer (A) means a value obtained by calculating the SPs of the structural units (structures in which vinyl groups have polymerized to form a single bond) derived from the monomers constituting the copolymer (A) using the SP calculation method described above, and calculating a weighted arithmetic mean based on the weight fractions of the constituent monomers at the time of preparation.
• the structural unit derived from methyl methacrylate consists of two CH 3 groups, one CH 2 group, one C atom, and one CO 2 group.
• the SP of the structural unit derived from methyl methacrylate is determined from the following equations to be 9.933 (cal/cm 3 ) 1/2 .
• the SP of a structural unit derived from ethyl methacrylate is determined to be 9.721 (cal/cm 3 ) 1/2 .
• the SP of the copolymer is determined by calculating a weighted arithmetic mean of the SPs of the monomer-derived structural units based on the weight fractions as shown below.
• the SP of the copolymer (A) can be adjusted to a desired range by suitably adjusting the monomers to be used or the weight fractions. Specifically, use of many monomers having a high-carbon number alkyl group can result in a lower SP, and use of many monomers having a low-carbon number alkyl group can result in a higher SP.
• the viscosity index improver composition of the present invention can be obtained by a known production method. Specific examples include a method involving solution polymerization of the monomers described above in a base oil (e.g., Fischer-Tropsch derived base oil (B) and/or a base oil other than the Fischer-Tropsch derived base oil (B) described later) in the presence of a polymerization catalyst.
• a base oil e.g., Fischer-Tropsch derived base oil (B) and/or a base oil other than the Fischer-Tropsch derived base oil (B) described later
• polymerization catalyst examples include azo catalysts (e.g., 2,2'-azobis(2-methylbutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile)), peroxide catalysts (e.g., benzoyl peroxide, cumyl peroxide, and lauryl peroxide), and redox catalysts (e.g., mixtures of benzoyl peroxide and tertiary amines).
• azo catalysts e.g., 2,2'-azobis(2-methylbutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile)
• peroxide catalysts e.g., benzoyl peroxide, cumyl peroxide, and lauryl peroxide
• redox catalysts e.g., mixtures of benzoyl peroxide and tertiary amines.
• a known chain transfer agent e.g., C2-C20 alkylmer
• the polymerization temperature is preferably 25°C to 140°C, more preferably 50°C to 120°C.
• the viscosity index improver composition can also be obtained by preparing the copolymer (A) by bulk polymerization, emulsion polymerization, or suspension polymerization instead of the solution polymerization in the base oil, and then dissolving the copolymer (A) in the base oil including the Fischer-Tropsch derived base oil (B) as necessary.
• the polymerization form of the copolymer (A) in the viscosity index improver composition may be a random addition polymer, or an alternating copolymer, and may be a graft copolymer, or a block copolymer.
• the viscosity index improver composition of the present invention contains a Fischer-Tropsch derived base oil (B) having a kinematic viscosity at 100°C of 4.0 mm 2 /s or less.
• Fischer-Tropsch derived means that the base oil is a synthetic product obtained by the Fischer-Tropsch process or the base oil is derived from a synthetic product obtained by the Fischer-Tropsch process.
• the Fischer-Tropsch process first produces synthesis gas (or "syngas”) containing carbon monoxide and hydrogen and then converts the gas into hydrocarbons using Fischer-Tropsch catalysts.
• oils obtained by producing synthesis gas from natural gas and converting it into hydrocarbons using Fischer-Tropsch catalysts are called gas-to-liquids (GTL) oils.
• Oils obtained by producing synthesis gas from coal and converting it into hydrocarbons using Fischer-Tropsch catalysts are called coal-to-liquids (CTL) oils.
• Oils obtained by producing synthesis gas from biomass and converting it into hydrocarbons using Fischer-Tropsch catalysts are called biomass-to-liquids (BTL) oils.
• the Fischer-Tropsch derived base oil (B) may be at least one base oil selected from the group consisting of a GTL oil, a CTL oil, and a BTL oil.
• the Fischer-Tropsch derived base oil (B) may be a GTL oil and/or a CTL oil or may be a GTL oil.
• the Fischer-Tropsch derived base oil (B) has a kinematic viscosity at 100°C (measured according to JIS-K2283 (2000)) (unit: mm 2 /s, hereinafter omitted) of 4.0 or less. With the kinematic viscosity at 100°C of the Fischer-Tropsch derived base oil (B) being 4.0 or less, the resulting viscosity index improver composition is less likely to form gels.
• the kinematic viscosity at 100°C of the Fischer-Tropsch derived base oil (B) is preferably 2.0 to 3.9, more preferably 2.4 to 3.5, particularly preferably 2.7 to 3.5.
• the Fischer-Tropsch derived base oil (B) preferably has a viscosity index (measured according to JIS-K2283 (2000)) of 100 or greater.
• the amount of the copolymer (A) in the viscosity index improver composition of the present invention is preferably 10 to 30 wt%, more preferably 15 to 25 wt% based on the weight of the viscosity index improver composition.
• the amount of the base oil other than the Fischer-Tropsch derived base oil (B) in the viscosity index improver composition of the present invention is preferably 78 wt% or less, more preferably 68 wt% or less based on the weight of the viscosity index improver composition.
• the ratio of the weight of the copolymer (A) to the weight of the Fischer-Tropsch derived base oil (B) ⁇ (A)/(B) ⁇ in the viscosity index improver composition of the present invention is preferably 0.05 to 10, more preferably 0.1 to 4.0, still more preferably 0.1 to 2.5, particularly preferably 0.1 to 1.1, most preferably 0.1 to 1.0.
• the amount of the (co)polymer (C) in the viscosity index improver composition of the present invention is preferably 0.01 to 30 wt%, more preferably 0.01 to 10 wt% based on the weight of the copolymer (A).
• the viscosity index improver composition of the present invention is less likely to form gels.
• a lubricating oil composition containing the viscosity index improver composition of the present invention can be suitably used in gear oils (e.g., differential oil and industrial gear oil), MTF, transmission fluids (e.g., ATF, DCTF, and belt-CVTF), traction fluids (e.g., toroidal-CVTF), shock absorber fluids, power steering fluids, hydraulic oils (e.g., construction machinery hydraulic oil and industrial hydraulic oil), and engine oils (for gasoline and diesel), particularly suitably used as a lubricating oil composition for internal combustion engines, particularly a lubricating oil composition for hybrid vehicles.
• gear oils e.g., differential oil and industrial gear oil
• MTF transmission fluids
• ATF, DCTF, and belt-CVTF traction fluids
• shock absorber fluids e.g., toroidal-CVTF
• shock absorber fluids e.g., toroidal-CVTF
• the components present in the Fischer-Tropsch derived base oil (B) are considered to affect the dimensions of the side chains derived from the monomer (a), a constituent monomer of the copolymer (A), and thereby further increases the viscosity index of the lubricating oil composition.
• the amount of the viscosity index improver composition in the lubricating oil composition is preferably 1.5% to 30 wt%, more preferably 2 to 20 wt% based on the weight of the lubricating oil composition.
• the amount of the copolymer (A) in the lubricating oil composition of the present invention is preferably 0.1 wt% or more and less than 10 wt%, more preferably 0.5 to 3 wt% based on the weight of the lubricating oil composition.
• the amount of the Fischer-Tropsch derived base oil (B) in the lubricating oil composition is preferably 0.4% to 27 wt%, more preferably 1 to 20 wt% based on the weight of the lubricating oil composition.
• the amount of the (co)polymer (C) in the lubricating oil composition of the present invention is preferably 0.01 to 5 wt% based on the weight of the lubricating oil composition.
• the amount of the base oil other than the Fischer-Tropsch derived base oil (B) in the lubricating oil composition is preferably 43% to 94 wt%, more preferably 57 to 93 wt% based on the weight of the lubricating oil composition.
• Examples of the additives in the present invention include the following.
• Examples include basic, overbased, or neutral metal salts (e.g., overbased metal salts or alkaline earth metal salts of sulfonates such as petroleum sulfonate, alkylbenzene sulfonate, and alkylnaphthalene sulfonate), salicylates, phenates, naphthenates, carbonates, phosphonates, and mixtures of detergents.
• basic, overbased, or neutral metal salts e.g., overbased metal salts or alkaline earth metal salts of sulfonates such as petroleum sulfonate, alkylbenzene sulfonate, and alkylnaphthalene sulfonate
• salicylates e.g., phenates, naphthenates, carbonates, phosphonates, and mixtures of detergents.
• Examples include long-chain fatty acids and their esters (e.g., oleic acid and its ester), long-chain amines and their amides (e.g., oleylamine and oleylamide).
• esters e.g., oleic acid and its ester
• long-chain amines and their amides e.g., oleylamine and oleylamide.
• Examples include silicone oils, metallic soap, fatty acid esters, and phosphate compounds.
• additives Only one of these additives may be added, or two or more additives may be added if necessary.
• a mixture of these additives which may be referred to as a performance additive or a package additive, may be added.
• the amount of each of these additives is preferably 0.1 to 15 wt% based on the total amount of the lubricating oil composition.
• the total amount of the additives is preferably 0.1 to 30 wt%, more preferably 0.3 to 20 wt%, still more preferably 3 to 10 wt% based on the total amount of the lubricating oil composition.
• the lubricating oil composition when used as an engine oil (0W-16), in terms of fuel economy, preferably has a viscosity index (measured according to JIS-K2283 (2000)) of 250 to 290, more preferably 260 to 280.
• the lubricating oil composition When the lubricating oil composition is used as an engine oil (0W-20), in terms of fuel economy, the lubricating oil composition preferably has a viscosity index (measured according to JIS-K2283 (2000)) of 300 to 330, more preferably 310 to 325.
• 0W-16 and 0W-20 mean that the oil has a viscosity corresponding to 0W-16 and 0W-20 respectively in the SAE standards ⁇ "0W” denotes a viscosity index under low-temperature/cold conditions (at start of engine) (winter grade), and “16" and “20” denote the viscosity of the engine oil when the engine has warmed up ⁇ .
• the lubricating oil composition when used as an engine oil (0W-16), in terms of fuel economy, preferably has a HTHS viscosity (100°C) (according to ASTM D4683) of 3.50 to 4.50 mPa ⁇ s, more preferably 3.60 to 4.30 mPa ⁇ s.
• the lubricating oil composition when used as an engine oil (0W-16), in terms of fuel economy, preferably has a kinematic viscosity (100°C) (measured according to JIS-K2283 (2000)) of 6.00 to 6.70 mm 2 /s, more preferably 6.10 to 6.60 mm 2 /s.
• the lubricating oil composition when used as an engine oil (0W-20), in terms of fuel economy, preferably has a kinematic viscosity (100°C) (measured according to JIS-K2283 (2000)) of 7.40 to 7.80 mm 2 /s, still more preferably 7.50 to 7.70 mm 2 /s.
• a kinematic viscosity 100°C (measured according to JIS-K2283 (2000)) of 7.40 to 7.80 mm 2 /s, still more preferably 7.50 to 7.70 mm 2 /s.
• the lubricating oil composition when used as an engine oil (0W-16), in terms of fuel economy, preferably has a kinematic viscosity (40°C) (measured according to JIS-K2283 (2000)) of 21.0 to 23.5 mm 2 /s, more preferably 21.2 to 23.0 mm 2 /s.
• the lubricating oil composition When the lubricating oil composition is used as an engine oil (0W-20), in terms of fuel economy, the lubricating oil composition preferably has a kinematic viscosity (40°C) (measured according to JIS-K2283 (2000)) of 22.0 to 25.0 mm 2 /s, more preferably 22.2 to 24.5 mm 2 /s.
• a kinematic viscosity 40°C
• the lubricating oil composition of the present invention is suitably used in gear oils (e.g., differential oil and industrial gear oil), MTF, transmission fluids (e.g., ATF, DCTF, and belt-CVTF), traction fluids (e.g., toroidal-CVTF), shock absorber fluids, power steering fluids, hydraulic oils (e.g., construction machinery hydraulic oil and industrial hydraulic oil), and engine oils (for gasoline and diesel), particularly suitably used as a lubricating oil composition for internal combustion engines, particularly a lubricating oil composition for hybrid vehicles.
• gear oils e.g., differential oil and industrial gear oil
• MTF transmission fluids
• ATF, DCTF, and belt-CVTF traction fluids
• shock absorber fluids e.g., toroidal-CVTF
• shock absorber fluids e.g., toroidal-CVTF
• power steering fluids e.g., hydraulic oils (e.g., construction machinery hydraulic oil and industrial hydraulic oil), and engine oils (for gasoline
• the disclosure (5) relates to the viscosity index improver composition according to the disclosure (4), wherein the copolymer (A) is a copolymer containing a monomer (d) represented by the following formula (2) as a constituent monomer: wherein R 3 is a hydrogen atom or a methyl group; -X 2 - is a group represented by -O- or -NH-; R 4 is a C2-C4 alkylene group; R 5 is a C1-C18 alkyl group or a C6-C20 aryl group; and q is an integer of 1 to 20, and each R 4 may be the same or different when q is 2 or greater.
• the copolymer (A) is a copolymer containing a monomer (d) represented by the following formula (2) as a constituent monomer: wherein R 3 is a hydrogen atom or a methyl group; -X 2 - is a group represented by -O- or -NH-; R 4 is a C
• the disclosure (7) relates to the viscosity index improver composition according to any one of the disclosures (1) to (6), wherein the copolymer (A) has a weight average molecular weight of 5,000 to 2,000,000.
• the disclosure (8) relates to the viscosity index improver composition according to any one of the disclosures (1) to (7), further comprising a base oil of API Groups I to V other than the Fischer-Tropsch derived base oil (B).
• a SUS pressure-resistant reaction vessel equipped with a temperature adjuster and a stirrer was charged with degassed and dehydrated hexane (400 parts by weight), tetrahydrofuran (1 part by weight), 1,3-butadiene (75 parts by weight), and n-butyllithium (2 parts by weight), followed by polymerization at a polymerization temperature of 70°C.
• ethylene oxide (2 parts by weight) was added.
• the mixture was reacted at 50°C for three hours.
• water 50 parts by weight
• a 1N aqueous hydrochloric acid solution 25 parts by weight
• the organic phase of the reaction solution was collected using a separating funnel, and heated to 70°C. Then, the solvent was removed under reduced pressure of 0.027 to 0.040 MPa over two hours.
• the resulting polybutadiene having a hydroxy group at one end was transferred to a reaction vessel equipped with a temperature adjuster, a stirrer, and a hydrogen inlet tube, and tetrahydrofuran (150 parts by weight) was added to uniformly dissolve the polybutadiene therein.
• tetrahydrofuran 150 parts by weight
• To the resulting solution was added a suspension obtained in advance by mixing palladium on carbon (10 parts by weight) and tetrahydrofuran (50 parts by weight). Then, the mixture was reacted at room temperature for eight hours while hydrogen was supplied at a flow rate of 30 mL/min through the hydrogen inlet tube into the solution. Subsequently, the palladium on carbon was filtered out.
• a hydrogenated polybutadiene polymer having a hydroxy group at one end (Y1-1) (total proportion of the isobutylene group and the 1,2-butylene group: 45 mol%; 1,2-adduct/1,4-adduct (molar ratio): 45/55; hydroxy value: 8.0 mgKOH/g; crystallization temperature: -60°C or lower) was obtained.
• a reaction vessel was charged with the hydrogenated polybutadiene polymer having a hydroxy group at one end (Y1-1) (245 parts by weight), methacrylic acid (245 parts by weight), and a sulfonic acid group-carrying inorganic porous material (acid value 45 mgKOH/g; particle size: 240 ⁇ m) (98 parts by weight), followed by esterification at 120°C. Then, the sulfonic acid group-carrying inorganic porous material was filtered out, and excess methacrylic acid was removed from the reaction solution under reduced pressure (0.027 to 0.040 MPa). Thus, a monomer (a-1) was obtained.
• the molecular weight of the resulting monomer (a-1) was measured by GPC, and the proportion of the 1,2-butylene group was measured by 13 C-NMR.
• a 1-L SUS pressure-resistant reaction vessel equipped with a temperature adjuster and a stirrer was charged with degassed and dehydrated hexane (400 parts by weight), tetrahydrofuran (1 part by weight), and n-butyllithium (0.4 parts by weight), followed by cooling to -40°C.
• 1,3-Butadiene (90 parts by weight) liquefied at -40°C was added thereto, and the mixture was polymerized at a polymerization temperature of -40°C.
• Example 1 a viscosity index improver composition (R-1) shown in Table 4, containing a copolymer (A-1) shown in Table 3, was obtained by the following method. First, a reaction vessel equipped with a stirrer, a heating and cooling device, a thermometer, and a nitrogen inlet tube was charged with a monomer blend for copolymer (A) production (100 parts by weight in total) shown in Table 3 and a base oil for polymerization (200 parts by weight in total) shown in Table 4.
• Viscosity index improver compositions (R-2 to R-17, S-1 to S-13) containing copolymers (A) were obtained as in Example 1, except that the amounts of the monomer blends and the polymerization catalysts were as shown in Table 3, and that the amounts of the base oils for polymerization and the diluent base oils were as shown in Table 4 to 12.

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