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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
• • 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
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
  • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
• • 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
  • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
  • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy compounds
  • C10M2207/2835—Esters of polyhydroxy compounds 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
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/071—Branched chain compounds
• • 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
  • C10N2030/54—Fuel economy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/02—Bearings
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to a polymer composition, a lubricating oil additive composition, and a lubricating oil composition. More specifically, the present invention relates to a polymer composition, a lubricating oil additive composition containing the polymer composition, and a lubricating oil composition containing the polymer composition.
• lubricating oil compositions used as drive system oils such as automatic transmission oils (ATF), continuously variable transmission oils (CVTF), shock absorber oils (SAF), internal combustion engine oils, hydraulic fluids, etc.
• ATF automatic transmission oils
• CVTF continuously variable transmission oils
• SAF shock absorber oils
• internal combustion engine oils hydraulic fluids, etc.
• Various properties are required depending on the application.
• fuel efficiency of automobiles in addition to the improvement of automobiles themselves, such as weight reduction of automobiles and improvement of engines, the suppression of friction loss in drive system equipment, etc., and the suppression of stirring loss and friction loss in internal combustion engines, etc. From this point of view, it is also important to reduce the viscosity of the lubricating oil composition.
• the higher the temperature the lower the viscosity of the liquid. Therefore, when the viscosity of the lubricating oil composition is lowered, the boundary lubrication region tends to increase in the high temperature range. As a result, problems such as increased wear are more likely to occur. Therefore, when reducing the viscosity of the lubricating oil composition, it is required that the viscosity does not decrease to the extent that the above problems occur in the high temperature range. In other words, lubricating oil compositions are required to have a high viscosity index.
• Viscosity index improvers are widely used as additives for imparting a high viscosity index to lubricating oil compositions.
• US Pat. No. 6,200,000 discloses comb polymers based on alkyl (meth)acrylates as viscosity index improvers.
• the present invention can impart a high viscosity index to a lubricating oil composition, and can reduce the HTHS viscosity at 80°C, which is the effective temperature range, while guaranteeing the viscosity required as the HTHS viscosity at 150°C. , to provide a polymer composition.
• Another object of the present invention is to provide a lubricating oil additive containing the polymer composition and a lubricating oil composition containing the polymer composition.
• [1] Containing a comb-shaped polymer (X) containing the following structural units (a) to (c) and a heteroatom-containing base oil (Y), Structural unit (a): a structural unit derived from a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms Structural unit (b): a long chain having 6 to 32 carbon atoms A structural unit derived from a long-chain alkyl (meth)acrylate (B) having a chain alkyl group, a structural unit (c): a structural unit derived from a macromonomer (C).
• Structural unit (a) a structural unit derived from a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms
• Structural unit (b) a long chain having 6 to 32 carbon atoms
• the polymer composition Based on all structural units of the polymer (X), it is 70% by mass or more, The polymer composition, wherein the heteroatom-containing base oil (Y) has a kinematic viscosity at 40° C. of 25 mm 2 /s or less.
• a lubricating oil additive composition containing the polymer composition according to [1] above.
• a lubricating oil composition comprising the polymer composition described in [1] above or the additive composition for lubricating oil described in [2] above, and a lubricating base oil (Z).
• a method for producing the polymer composition according to [1] above A short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms, a long-chain alkyl (meth)acrylate (B) having a long-chain alkyl group having 6 to 32 carbon atoms, a step (S1) of polymerizing a macromonomer (C) to produce a comb-shaped polymer (X); a step (S2) of dissolving the comb polymer (X) in the heteroatom-containing base oil (Y),
• the blending amount of the short-chain alkyl (meth)acrylate (A) is such that the short-chain alkyl (meth)acrylate (A), the long-chain alkyl (meth)acrylate (B), and the macro Based on the total amount of the monomer (C), it is 70% by mass or more,
• the present invention it is possible to impart a high viscosity index to a lubricating oil composition, and reduce the HTHS viscosity at 80°C, which is the effective temperature range, while ensuring the required viscosity as the HTHS viscosity at 150°C. It is possible to provide a polymer composition.
• (meth)acrylate means acrylate or methacrylate, and other similar terms have the same meaning.
• the polymer composition of this embodiment contains a comb-shaped polymer (X) containing the following structural units (a) to (c), and a heteroatom-containing base oil (Y).
• Structural unit (a) a structural unit derived from a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms
• Structural unit (b) a long chain having 6 to 32 carbon atoms
• Structural unit (c) Structural unit derived from macromonomer (C) It is 70% by mass or more based on all structural units of the polymer (X).
• the heteroatom-containing base oil (Y) has a kinematic viscosity of 25 mm 2 /s or less at 40°C.
• the present inventors have made intensive studies to solve the above problems. As a result, the inventors have found that the polymer composition having the above constitution can solve the above problems. Although the reason why the polymer composition having the above configuration can solve the above problems is not clear, it is presumed, for example, for the following reasons.
• the comb polymer (X) is composed only of the structural unit (a) derived from the monomer (A), the structural unit (b) derived from the monomer (B), and the structural unit (c) derived from the monomer (C).
• other structural units other than the structural units (a), (b), and (c) may be included within a range that does not impair the effects of the present invention.
• the total content of the structural units (a), (b), and (c) in the comb polymer (X) is preferably 70 mol % to 70 mol % based on the total structural units of the comb polymer (X). 100 mol %, more preferably 80 mol % to 100 mol %, still more preferably 90 mol % to 100 mol %.
• the monomers (A) to (C) will be described in detail below.
• the monomer (A) used in this embodiment is a short-chain alkyl (meth)acrylate having a short-chain alkyl group with 1 to 5 carbon atoms.
• Easy comb polymer (X) can be prepared.
• monomer (A) may be used individually by 1 type, and may be used in combination of 2 or more type. Therefore, the comb-shaped polymer (X) may contain one type of structural unit (a) derived from the monomer (A), or may contain two or more types.
• the monomer (A) preferably contains a monomer (A1) represented by the following general formula (a-1) from the viewpoint of making it easier to exhibit the effects of the present invention. That is, the structural unit (a) preferably contains a structural unit (a1) derived from the monomer (A1).
• R a1 is a hydrogen atom or a methyl group.
• Monomers in which R a1 is a substituent other than a hydrogen atom and a methyl group are difficult to obtain, and their low reactivity makes it difficult to polymerize them.
• R a1 is preferably a methyl group.
• R a3 represents a short-chain alkyl group having 1 to 5 carbon atoms. If the number of carbon atoms in the short-chain alkyl group is 6 or more, the effects of the present invention are difficult to achieve.
• Short-chain alkyl groups having 1 to 5 carbon atoms that can be selected as R a3 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, and the like. is mentioned.
• the number of carbon atoms in the short-chain alkyl group that can be selected as R a3 is preferably 2 or more and 4 or less, more preferably 3 or more and 4 or less, and still more preferably 4.
• X a1 represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, —O—, or —NH—.
• R a2 is a linear or branched alkylene group having 2 to 4 carbon atoms
• ma1 is an integer of 0-20.
• multiple (R a2 O) ma1 moieties may be the same or different.
• Examples of preferred compounds as the monomer (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , tert-butyl (meth)acrylate, etc. Among these, n-butyl (meth)acrylate is preferred.
• the structural unit (a1) derived from the monomer (A1) may contain one type alone or may contain two or more types.
• the content of the structural unit (a1) is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, and still more preferably, based on all structural units of the structural unit (a). is 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %, still more preferably 90 mol % to 100 mol %.
• the monomer (B) used in this embodiment is a long-chain alkyl (meth)acrylate having a long-chain alkyl group with 6 to 32 carbon atoms.
• the structural unit (b) derived from the monomer (B) mainly functions to exhibit oil solubility in the comb polymer (X).
• monomer (B) may be used individually by 1 type, and may be used in combination of 2 or more type. Therefore, the comb-shaped polymer (X) may contain one type of structural unit (b) derived from the monomer (B), or may contain two or more types.
• the monomer (B) preferably contains a monomer (B1) represented by the following general formula (b-1) from the viewpoint of making it easier to exhibit the effects of the present invention. That is, the structural unit (b) preferably contains a structural unit (b1) derived from the monomer (B1).
• R b1 is a hydrogen atom or a methyl group.
• Monomers in which R b1 is a substituent other than a hydrogen atom and a methyl group are difficult to obtain, and their low reactivity makes it difficult to polymerize them.
• R b1 is preferably a methyl group.
• R b3 represents a long-chain alkyl group having 6 to 32 carbon atoms.
• the number of carbon atoms in the long-chain alkyl group is less than 6 or more than 32, oil-solubility is hardly exhibited.
• Examples of long-chain alkyl groups having 6 to 32 carbon atoms that can be selected as R b3 include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Linear or branched alkyl groups such as nonadecyl group, eicosyl group, tetracosyl group and 2-decyltetradecyl group can be mentioned.
• R b3 is a branched long-chain alkyl group
• the long-chain alkyl group preferably has 8 to 32 carbon atoms.
• the number of carbon atoms in the long-chain alkyl group is preferably 10 or more and 20 or less, more preferably 10 or more and 16 or less, from the viewpoint of making it easier to exhibit the effects of the present invention.
• X b1 represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, —O—, or —NH—. From the viewpoint of making it easier to exhibit the effects of the present invention, X b1 is preferably —O—.
• Rb2 is a linear or branched alkylene group having 2 to 4 carbon atoms
• mb1 is an integer of 0-20.
• mb1 is 2 or more, multiple (R b2 O) mb1 moieties may be the same or different.
• Examples of preferred compounds as the monomer (B1) include n-decyl (meth)acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate. , n-pentadecyl (meth) acrylate, n-hexadecyl (meth) acrylate, etc.
• n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate are preferred, n-dodecyl (meth) acrylate and n-tridecyl (meth)acrylate are more preferably used in combination.
• the structural unit (b1) derived from the monomer (B1) may contain one type alone or may contain two or more types.
• the content of the structural unit (b1) is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, still more preferably based on the total structural units of the structural unit (b). is 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %, still more preferably 90 mol % to 100 mol %.
• a "comb-shaped polymer” has a structure in which a main chain has a plurality of trident branching points from which high-molecular-weight side chains exit.
• the monomer (C) used in this embodiment is a macromonomer essential for forming the structure of the comb polymer. That is, the high-molecular-weight side chains of the monomer (C) become the high-molecular-weight side chains of the comb-shaped polymer (X), forming a characteristic structure of the comb-shaped polymer.
• monomer (C) may be used individually by 1 type, and may be used in combination of 2 or more type. Therefore, the comb-shaped polymer (X) may contain one type of structural unit (c) derived from the monomer (C), or may contain two or more types.
• the number average molecular weight (Mn) of the monomer (C) is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, from the viewpoint of base oil solubility, viscosity index, and shear stability. ,000 or more, preferably 50,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.
• the monomer (C) preferably contains a monomer (C1) represented by the following general formula (c-1) from the viewpoint of making it easier to exhibit the effects of the present invention. That is, the structural unit (c) preferably contains a structural unit (c1) derived from the monomer (C1).
• R c1 is a hydrogen atom or a methyl group.
• Monomers in which R c1 is a substituent other than a hydrogen atom and a methyl group are difficult to obtain, and their low reactivity makes it difficult to polymerize them. From the viewpoint of making it easier to exhibit the effects of the present invention, R c1 is preferably a methyl group.
• R c3 corresponds to a high-molecular-weight side chain of the comb-shaped polymer (X) and is a polymer containing repeating units of alkylene groups.
• the alkylene group may be linear or branched, but from the viewpoint of suppressing crystallization at low temperatures and preventing thickening when used as a viscosity index improver, the branched chain preferably in the form of
• the branched hydrocarbon group preferably contains a branched alkylene group as a repeating unit, and more preferably contains both a branched alkylene group and a linear alkylene group as repeating units.
• Branched alkylene groups include 1,2-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene and 1,2-hexylene groups.
• Linear alkylene groups include ethylene, 1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group and the like.
• polymers having repeating units that are 1,2-butylene groups and/or 1,4-butylene groups are more preferable.
• the number of carbon atoms in the hydrocarbon group of R c3 is preferably 35 or more, more preferably 50 or more, still more preferably 70 or more, still more preferably 100 or more, preferably 3500 or less, more preferably 1500 or less, 700 or less is more preferable.
• X c1 represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, —O—, or —NH—. From the viewpoint of making it easier to exhibit the effects of the present invention, X c1 is preferably —O—.
• R c2 is a linear or branched alkylene group having 2 to 4 carbon atoms
• constituent units derived from the macromonomer (C) contained in the comb-shaped polymer (A) may be of one type alone, or may be of two or more types.
• the content of the structural unit (c1) is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, and still more preferably based on the total structural units of the structural unit (c). is 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %, still more preferably 90 mol % to 100 mol %.
• the content (% by mass) of the structural unit (a) derived from the monomer (A) is required to be 70% by mass or more based on the total structural units of the comb polymer (X). If the content of the structural unit (a) is less than 70% by mass, it becomes difficult to reduce the HTHS viscosity in the effective temperature range (80°C). From the viewpoint of easily reducing the HTHS viscosity in the effective temperature range (80° C.), the content of the structural unit (a) is preferably 72% by mass or more, based on the total structural units of the comb polymer (X). More preferably 75% by mass or more, still more preferably 80.0% by mass or more.
• the content is preferably 90% by mass or less, more preferably 85% by mass or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 72% by mass to 90% by mass, more preferably 75% by mass to 90% by mass, and still more preferably 80% by mass to 85% by mass.
• the content (mol%) of the structural unit (a) derived from the monomer (A) is the comb polymer (X) from the viewpoint of making it easier to reduce the HTHS viscosity in the effective temperature range (80°C).
• the comb polymer (X) Based on all structural units of, preferably 90.0 mol% or more, more preferably 91.0 mol% or more, still more preferably 92.0 mol% or more, even more preferably 93.0 mol or more, still more preferably It is 94.0 mol % or more, more preferably 95 mol % or more.
• the viscosity index it is preferably 97.0 mol % or less, more preferably 96.0 mol % or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, preferably 90.0 mol% to 97.0 mol%, more preferably 91.0 mol% to 97.0 mol%, still more preferably 92.0 mol% to 97.0 mol%, more It is more preferably 93.0 mol % to 96.0 mol %, still more preferably 94.0 mol % to 96.0 mol %, still more preferably 95.0 mol % to 96.0 mol %.
• the content ratio of each structural unit in the comb-shaped polymer (X) usually corresponds to the ratio (feed ratio) of each monomer constituting the comb-shaped polymer (X).
• the content (% by mass) of the structural unit (b) derived from the monomer (B) is preferably 3 mass based on all structural units of the comb polymer (X) from the viewpoint of ensuring oil solubility.
• % or more more preferably 4% by mass or more, and still more preferably 5% by mass or more.
• it is preferably 12% by mass or less, more preferably 10% by mass or less, and still more preferably 9% by mass or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 3% by mass to 12% by mass, more preferably 4% by mass to 10% by mass, and still more preferably 5% by mass to 9% by mass.
• the content (mol %) of the structural unit (b) derived from the monomer (B) is preferably 3.0% based on the total structural units of the comb polymer (X) from the viewpoint of ensuring oil solubility. It is 0 mol % or more, more preferably 3.5 mol % or more, and preferably 7.0 mol % or less, more preferably 6.5 mol % or less, still more preferably 6.0 mol % or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, the be.
• the content (% by mass) of the structural unit (c) derived from the monomer (C) is based on the total structural units of the comb polymer (X) from the viewpoint of making it easier to exhibit the effects of the present invention.
• it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 5% to 25% by mass, more preferably 7% to 20% by mass, and still more preferably 10% to 15% by mass.
• the content (mol%) of the structural unit (c) derived from the monomer (C) is based on the total structural units of the comb polymer (X), from the viewpoint of making it easier to exhibit the effects of the present invention.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 0.1 mol % to 2.0 mol %, more preferably 0.2 mol % to 1.0 mol %, still more preferably 0.25 mol % to 0.5 mol %. .
• the comb-shaped polymer (X) contains structural units derived from other monomers, in addition to the structural units (a), (b), and (c), within a range that does not impair the effects of the present invention. good too.
• Such other monomers include functional group-containing monomers other than monomers (A), (B), and (C).
• Such other functional group-containing monomers include, for example, functional group-containing (meth)acrylates other than the monomers (A), (B), and (C).
• Such functional group-containing (meth)acrylates include methoxyethyl (meth)acrylate, methylthiomethyl (meth)acrylate, cyanoethyl (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl A methacrylate etc. are mentioned.
• the comb-shaped polymer (X) contains structural units derived from functional group-containing monomers other than the monomers (A), (B), and (C).
• the comb polymer (X) of the present embodiment preferably has a mass average molecular weight (Mw) of 100,000 or more, more preferably 120,000 or more, and still more preferably 140,000 or more. Also, it is preferably 900,000 or less, more preferably 870,000 or less, and still more preferably 850,000 or less. The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 100,000 to 900,000, more preferably 120,000 to 870,000, and still more preferably 140,000 to 850,000.
• the comb polymer (X) of the present embodiment has a molecular weight distribution (Mw/Mn) of preferably 3.50 or less, more preferably 3.20 or less, and even more preferably 3.00 or less. Moreover, it is usually 1.01 or more.
• Mw/Mn molecular weight distribution
• the polymerization mode of the comb-shaped polymer (X) of the present embodiment is not particularly limited, and may be block copolymerization, random copolymerization, or block/random copolymerization.
• Heteroatom-containing base oil (Y) contains a heteroatom-containing base oil (Y).
• Y the heteroatom-containing base oil
• the comb-shaped polymer (X) can be adjusted to a state in which its performance is easily exhibited.
• the heteroatom-containing base oil (Y) is a base oil composed of a compound containing a heteroatom in its molecular skeleton.
• heteroatom refers to atoms other than carbon and hydrogen, such as nitrogen, oxygen and sulfur atoms.
• heteroatom-containing base oils (Y) include alcohols, esters, ethers, amides, ketones, thioethers and the like.
• the heteroatom-containing base oil (Y) is preferably one or more selected from the group consisting of esters, ethers, amides, ketones, and thioethers, more preferably esters, from the viewpoint of the effects of the present invention. , ethers, and amides, and more preferably esters from the viewpoint of availability.
• esters examples include various esters such as monoesters, diesters, and polyesters.
• Monoesters include, for example, decyl decanoate and 2-ethylhexyl caprylate.
• diesters include bis(2-ethylhexyl) sebacate, bis(2-ethylhexyl) adipate, and dibutyl adipate.
• polyesters include complete esters or partial esters of trivalent or higher polyhydric alcohols such as trimethylolpropane and carboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. be done.
• the polyester is preferably one or more selected from full esters of trimethylolpropane and partial esters of trimethylolpropane, more preferably full esters of trimethylolpropane and one or more selected from stearic acid and lauric acid. and one or more selected from partial esters of trimethylolpropane and one or more selected from stearic acid and lauric acid, more preferably trimethylolpropane and one or more selected from stearic acid and lauric acid. esters. Among the above esters, one or more selected from the group consisting of bis(2-ethylhexyl) sebacate, bis(2-ethylhexyl) adipate, and trimethylolpropane ester are preferred.
• the ether examples include bis(2-ethylhexyl) ether and polyvinyl ether.
• polyvinyl ether trimers to pentamers of polyvinyl ether are preferable.
• bis(2-ethylhexyl) ether is preferred.
• amide examples include N,N-di(2-ethylhexyl)-2-ethylhexanamide and the like.
• the heteroatom-containing base oil (Y) should have a kinematic viscosity at 40° C. of 25 mm 2 /s or less. If the 40° C. kinematic viscosity exceeds 25 mm 2 /s, the viscosity index of the comb polymer (X) may not be sufficiently improved.
• the 40° C. kinematic viscosity of the heteroatom-containing base oil (Y) is preferably 20 mm 2 /s or less, more preferably 15 mm 2 /s or less, from the viewpoint of making it easier to improve the viscosity index of the comb polymer (X). It is preferably 12 mm 2 /s or less.
• it is preferably 1.5 mm 2 /s or more, more preferably 3.0 mm 2 /s or more, and even more preferably 5.0 mm 2 /s or more.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 1.5 mm 2 /s to 20 mm 2 /s, more preferably 3.0 mm 2 /s to 15 mm 2 /s, still more preferably 5.0 mm 2 /s to 12 mm 2 /s. .
• a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms and a long-chain alkyl group having 6 to 32 carbon atoms are combined.
• the blending amount of the short-chain alkyl (meth)acrylate (A) is such that the short-chain alkyl (meth)acrylate (A), the long-chain alkyl (meth)acrylate (B), and the macro Based on the total amount of the monomer (C), it is 70% by mass or more
• the production method is such that the heteroatom-containing base oil (Y) has a kinematic viscosity at 40° C. of 25 mm 2 /s or less.
• a comb-shaped polymer (X) is produced.
• the comb-shaped polymer (X) comprises a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms and a long-chain alkyl (meth)acrylate (A) having a long-chain alkyl group having 6 to 32 carbon atoms.
• Acrylate (B) and macromonomer (C) can be obtained, for example, by radical polymerization.
• polymerization method conventionally known methods such as solution polymerization method, emulsion polymerization method, suspension polymerization method, reverse phase suspension polymerization method, thin film polymerization method, and spray polymerization method can be used.
• a solution polymerization method is preferred, and it can be obtained by radically polymerizing the monomer (A), the monomer (B), and the monomer (C) in a solvent.
• the comb-shaped polymer (X) When the comb-shaped polymer (X) is produced by solution polymerization, it can be obtained by radically polymerizing the monomer (A), the monomer (B), and the monomer (C) in a polymerization solvent using a polymerization initiator.
• the blending amount of the monomer (A) is based on the total amount of the monomers (A) to (C) (when the comb-shaped polymer (X) also contains structural units derived from other monomers, the monomers (A) to (C) and other (Based on the total amount of monomers), it must be 70% by mass or more. If the amount of the monomer (A) is less than 70% by mass, the content of the structural unit (a) in the comb polymer (X) cannot be 90 mol% or more.
• the amount of the monomer (A) blended is preferably 72% by mass or more, based on the total amount of the monomers (A) to (C). More preferably 75% by mass or more, still more preferably 80.0% by mass or more.
• the content is preferably 90% by mass or less, more preferably 85% by mass or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 72% by mass to 90% by mass, more preferably 75% by mass to 90% by mass, and still more preferably 80% by mass to 85% by mass.
• the blending amount of the monomer (B) is based on the total amount of the monomers (A) to (C) (the comb polymer (X) is derived from another monomer) from the viewpoint of ensuring the oil solubility of the comb polymer (X).
• the total amount of monomers (A) to (C) and other monomers) is preferably 3% by mass or more, more preferably 4% by mass or more, and still more preferably 5% by mass or more. be. Also, it is preferably 12% by mass or less, more preferably 10% by mass or less, and still more preferably 9% by mass or less. The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 3% by mass to 12% by mass, more preferably 4% by mass to 10% by mass, and still more preferably 5% by mass to 9% by mass.
• the blending amount of the monomer (C) is based on the total amount of the monomers (A) to (C) (the comb-shaped polymer (X) is derived from other monomers) from the viewpoint of making it easier to exhibit the effects of the present invention.
• the total amount of monomers (A) to (C) and other monomers) is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more. . Also, it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 5% to 25% by mass, more preferably 7% to 20% by mass, and still more preferably 10% to 15% by mass.
• a heteroatom-containing base oil (Y) is preferably used as the polymerization solvent.
• a comb-shaped polymer (X) that more easily exhibits the effects of the present invention can be obtained.
• the content of the structural unit (a) derived from the monomer (A) can be easily increased, the effect of reducing the HTHS viscosity in the effective temperature range (80°C) can be easily obtained.
• the comb-shaped polymer (X) is obtained using a solvent other than the heteroatom-containing base oil (Y), the comb-shaped polymer (X) and the heteroatom-containing base oil (Y ), it has been confirmed that the same effects as in the case of using the heteroatom-containing base oil (Y) as a polymerization solvent can be obtained. Therefore, in this embodiment, a polymerization solvent other than the heteroatom-containing base oil (Y) may be used.
• the polymerization solvent other than the heteroatom-containing base oil (Y) may be a solvent in which the above-mentioned monomers are dissolved, and aromatic hydrocarbon solvents such as mineral oil, toluene, xylene, and alkylbenzene having 9 to 10 carbon atoms; Aliphatic hydrocarbon solvents having 5 to 18 carbon atoms such as pentane, hexane, heptane, cyclohexane and octane can be used.
• polymerization initiator examples include one or more selected from the group consisting of azo initiators, peroxide initiators, redox initiators, and organic halogen compound initiators.
• the polymerization initiator is preferably one or more selected from azo initiators and peroxide initiators, more preferably one or more selected from azo initiators and organic peroxides, still more preferably organic peroxides. Oxides can be used.
• azo polymerization initiators examples include 2,2′-azobis(isobutyronitrile) (abbreviation: AIBN), 2,2′-azobis(2-methylbutyronitrile) (abbreviation: AMBN), 2, 2′-azobis(2,4-dimethylvaleronitrile) (abbreviation: ADVN), 4,4′-azobis(4-cyanovaleric acid) (abbreviation: ACVA) and salts thereof (for example, hydrochloride etc.), dimethyl 2, 2'-azobis isobutyrate, 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and the like. .
• AIBN 2,2′-azobis(isobutyronitrile)
• AMBN 2,2′-azobis(2-methylbutyronitrile)
• ADVN 2, 2′-azobis(2,4-dimethylvaleronitrile)
• peroxide-based initiators include inorganic peroxides and organic peroxides.
• inorganic peroxides include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.
• organic peroxides include benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, succinic peroxide, di(2-ethoxyethyl)peroxydicarbonate, and tert-butyl peroxypivalate.
• tert-hexyl peroxypivalate tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate
• tert-butyl peroxy 2-ethylhexanoate tert-butyl peroxyisobutyrate
• tert-amylperoxy 2-ethylhexanoate 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate
• dibutylperoxytrimethyladipate 2,2-bis(4,4-di- t-butylperoxycyclohexyl)propane, lauryl peroxide, and the like.
• redox initiators include alkali metal sulfites or bisulfites (e.g., ammonium sulfite, ammonium bisulfite, etc.), reducing agents such as ferrous chloride, ferrous sulfate, and ascorbic acid, and alkali metal persulfates.
• alkali metal sulfites or bisulfites e.g., ammonium sulfite, ammonium bisulfite, etc.
• reducing agents such as ferrous chloride, ferrous sulfate, and ascorbic acid
• alkali metal persulfates examples include a combination with an oxidizing agent such as a salt, ammonium persulfate, hydrogen peroxide, or an organic peroxide.
• the amount of polymerization initiator to be used can be appropriately selected in consideration of the physical properties of the desired polymer (for example, adjustment of molecular weight, etc.).
• chain transfer agent In the radical polymerization, if necessary, a known chain transfer agent may be used for the purpose of adjusting physical properties of the polymer such as molecular weight.
• chain transfer agents include mercaptans, thiocarboxylic acids, secondary alcohols such as isopropanol, amines such as dibutylamine, hypophosphites such as sodium hypophosphite, chlorine-containing compounds, and alkylbenzene compounds.
• Mercaptans include alkyl groups having 2 to 20 carbon atoms such as n-butyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan and tert-dodecyl mercaptan.
• Alkyl mercaptan compounds having a Thiocarboxylic acids include, for example, thioglycolic acid and thiomalic acid.
• the amount of chain transfer agent to be used can be appropriately selected in consideration of the physical properties of the desired polymer (for example, adjustment of molecular weight, etc.).
• Polymerization control methods include an adiabatic polymerization method and a temperature control polymerization method.
• the reaction temperature during polymerization is preferably 30 to 140°C, more preferably 50 to 130°C, still more preferably 70 to 120°C.
• a method of initiating polymerization by irradiating radiation, electron beams, ultraviolet rays, or the like can also be employed.
• Preferred is a temperature-controlled solution polymerization method.
• step (S2) comb-shaped polymer (X) is dissolved in heteroatom-containing base oil (Y) to produce a polymer composition containing comb-shaped polymer (X) and heteroatom-containing base oil (Y).
• step (S1) when the heteroatom-containing base oil (Y) is used as the polymerization solvent, the comb-shaped polymer (X) is dissolved in the heteroatom-containing base oil (Y) without removing the polymerization solvent. Therefore, step (S2) can be omitted.
• the step (S2) may be carried out from the viewpoint of adjusting the content of the heteroatom-containing base oil (Y).
• step (S2) can be selected depending on the polymerization solvent used in step (S1), and when the heteroatom-containing base oil (Y) is used as the polymerization solvent, Step (S2) may or may not be performed.
• the step (S2) is always carried out.
• the heteroatom-containing base oil as the polymerization solvent in the step (S1) (Y) may not be used, and step (S2) may not be performed.
• the polymer composition of this embodiment contains a comb polymer (X) and a heteroatom-containing base oil (Y).
• the content of the comb polymer (X) in terms of resin content is based on the total amount of the polymer composition, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, still more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass It is below.
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 0.1% by mass to 50% by mass, more preferably 1.0% by mass to 40% by mass, and still more preferably 5.0% by mass to 30% by mass.
• the polymer composition contains the heteroatom-containing base oil (Y). It may contain the comb-shaped polymer (X) and a base oil other than the heteroatom-containing base oil (Y) without containing it.
• the content (% by mass) of the structural unit (a) derived from the monomer (A) is required to be 70% by mass or more based on the total structural units of the comb polymer (X), as described above. From the viewpoint of making it easier to reduce the HTHS viscosity in the effective temperature range (80 ° C.), the content (% by mass) of the structural unit (a) derived from the monomer (A) is It is preferably 71% by mass or more, more preferably 72% by mass or more, based on the structural unit.
• the content is preferably less than 77% by mass, more preferably 75% by mass or less, and even more preferably 74% by mass or less.
• the content (mol%) of the structural unit (a) derived from the monomer (A) is 90.0 mol% or more, preferably 91.0 mol% or more, based on the total structural units of the comb polymer (X), More preferably 92.0 mol % or more, still more preferably 93.0 mol % or more. Moreover, it is preferably 95.0 mol % or less.
• the content (% by mass) of the structural unit (b) derived from the monomer (B) is, from the viewpoint of ease of polymerization of the comb polymer (X) and ensuring the oil solubility of the comb polymer (X), It is preferably more than 5% by mass, more preferably 6% by mass or more, and even more preferably 7% by mass or more based on the total structural units of the comb polymer (X). Also, it is preferably 11% by mass or less, more preferably 10% by mass or less, and still more preferably 9% by mass or less.
• the content (mol %) of the structural units (b) derived from the monomer (B) is preferably 5.0 mol % or more based on the total structural units of the comb polymer (X). Also, it is preferably 8.0 mol % or less, more preferably 7.0 mol % or less, and still more preferably 6.0 mol % or less.
• the content (% by mass) of the structural unit (c) derived from the monomer (C) is determined from the viewpoint of the ease of polymerization of the comb polymer (X) and from the viewpoint of making it easier to exhibit the effects of the present invention. It is preferably more than 15% by mass, more preferably 16% by mass or more, still more preferably 17% by mass or more, and still more preferably 18% by mass or more based on the total structural units of the polymer (X). Also, it is preferably 22% by mass or less, more preferably 21% by mass or less, and still more preferably 20% by mass or less.
• the content (mol%) of the structural unit (c) derived from the monomer (C) is preferably 0.4 mol% or more based on the total structural units of the comb polymer (X). Also, it is preferably 0.7 mol % or less, more preferably 0.6 mol % or less.
• the content ratio of each structural unit in the comb polymer (X) usually matches the ratio (feed ratio) of each monomer constituting the comb polymer (X). Therefore, the content of each of the structural units (a) to (c) (based on all structural units of the comb polymer (X)) is (When the comb-shaped polymer (X) also contains structural units derived from other monomers, the total amount of monomers (A) to (C) and other monomers).
• the polymer composition of the present embodiment can impart a high viscosity index to lubricating oil compositions. Therefore, it is useful as a viscosity index improver.
• a method of use of the polymer composition of this embodiment as a viscosity index improver composition is provided.
• the lubricating oil composition of the present embodiment contains a polymer composition containing the comb polymer (X) and a lubricating base oil.
• the content of the comb-shaped polymer (X) is preferably based on the total amount of the lubricating oil composition. It is adjusted to 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more.
• the content of the comb-shaped polymer (X) is adjusted to preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the lubricating oil composition. .
• the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 12% by mass, and still more preferably 0.3% by mass to 10% by mass.
• lubricating base oil general base oils used in lubricating oil compositions can be used without particular limitation. Specifically, for example, one or more selected from the group consisting of mineral oil and synthetic oil.
• the kinematic viscosity at 100 ° C. of the lubricating base oil is preferably in the range of 1 mm 2 / s to 50 mm 2 / s, more preferably in the range of 2 mm 2 / s to 30 mm 2 / s, 3 mm 2 / s It is more preferably in the range of ⁇ 20 mm 2 /s.
• the viscosity index of the lubricating base oil is preferably 80 or higher, more preferably 90 or higher, and even more preferably 100 or higher.
• the kinematic viscosity and viscosity index of the lubricating base oil are values measured or calculated according to JIS K2283:2000.
• lubricating base oils include, for example, distillates obtained by atmospheric distillation and/or vacuum distillation of paraffin-based crude oils, intermediate-based crude oils, or naphthenic-based crude oils; oil; and the like.
• Refining methods for obtaining refined oil include, for example, solvent dewaxing, hydroisomerization, hydrofinishing, and clay treatment.
• Synthetic oils include, for example, hydrocarbon oils, aromatic oils, ester oils, ether oils and the like.
• GTL Gas To Liquids
• GTL wax Gas To Liquids WAX
• the polymer composition of the present embodiment even when a lubricating base oil containing mineral oil is used, the polymer composition dissolves well in the lubricating base oil, and the effect can be exhibited.
• a base oil other than the heteroatom-containing base oil (Y) is used as the polymerization solvent for the comb polymer (X), and the diluent solvent for the polymer composition is also a base oil other than the heteroatom-containing base oil (Y).
• the lubricating base oil constituting the lubricating oil composition contains the heteroatom-containing base oil (Y).
• the content of the heteroatom-containing base oil (Y) in the lubricating base oil is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass, based on the total amount of the lubricating base oil. % by mass or more.
• the lubricating base oil constituting the lubricating oil composition contains the heteroatom-containing base oil (Y)
• the lubricating base oil may consist only of the heteroatom-containing base oil (Y)
• a base oil other than the heteroatom-containing base oil (Y) for example, mineral oil
• the content of the base oil (e.g., mineral oil) other than the heteroatom-containing base oil (Y) in the lubricating base oil is preferably 95% by mass or less, more preferably, based on the total amount of the lubricating base oil. It is 92% by mass or less, more preferably 90% by mass or less.
• the lubricating oil composition of the present embodiment contains antioxidants, oiliness agents, detergent-dispersants, viscosity index improvers, rust inhibitors, metal deactivators, and Other additives such as antifoaming agents may be included. These may be used individually by 1 type, and may be used in combination of 2 or more type.
• additives other than the polymer composition containing the comb-shaped polymer (X) an antioxidant, an oily agent, a detergent-dispersant
• Additive packages for lubricating oil compositions containing one or more additives selected from additives, viscosity index improvers, rust inhibitors, metal deactivators, antifoam agents, and the like are also provided.
• antioxidant As the antioxidant, amine-based antioxidants, phenol-based antioxidants, and the like, which are used in conventional lubricating oil compositions, can be used. These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.
• amine antioxidants include monoalkyldiphenylamine compounds such as monooctyldiphenylamine and monononyldiphenylamine; ,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; dialkyldiphenylamine compounds; tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; Polyalkyldiphenylamine compounds; ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, butylphenyl- ⁇ -naphthylamine, pentylphenyl- ⁇ -naphthylamine, hexylphenyl- ⁇ -naphthylamine, h
• phenolic antioxidants include monophenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; -methylenebis (2,6-di-tert-butylphenol) and 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) and other bisphenol compounds.
• Add the minimum amount necessary to maintain the oxidative stability of the product is preferably 0.01 to 1% by mass based on the total amount of the lubricating oil composition.
• oiliness agent Fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters and glycerides; and amine compounds such as aliphatic amines can be used as the oiliness agent.
• the content of the oily agent is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of addition effect.
• Detergent-dispersants include metal sulfonates, metal salicylates, metal phenates, succinimides, and the like.
• the content of the detergent-dispersant is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of addition effect.
• viscosity index improver examples include non-dispersed polymethacrylates, dispersed polymethacrylates, olefinic copolymers (e.g., ethylene-propylene copolymers), dispersed olefinic copolymers, and styrene copolymers. (eg, styrene-diene hydrogenated copolymer, etc.).
• the content of the viscosity index improver is preferably 0.3 to 5% by mass based on the total amount of the lubricating oil composition.
• (anti-rust) Rust inhibitors include metal sulfonates, succinate esters, and alkanolamines such as alkylamines and monoisopropanolamine.
• the content of the rust preventive is usually 0.01 to 5% by mass, preferably 0.03 to 3% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
• metal deactivator examples include benzotriazole and thiadiazole.
• a preferable content of the metal deactivator is usually 0.01 to 5% by mass, preferably 0.01 to 1% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of adding effect.
• Antifoaming agents include methylsilicone oil, fluorosilicone oil, polyacrylate, and the like.
• the content of the antifoaming agent is usually 0.0005 to 0.01% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
• the 100° C. kinematic viscosity of the lubricating oil composition of the present embodiment is preferably from 4.0 mm 2 /s to 12.5 mm 2 / s, more preferably from the viewpoint of improving lubricating performance, viscosity characteristics, and fuel economy. 4.5 mm 2 /s to 11.0 mm 2 /s, more preferably 5.0 mm 2 /s to 10.0 mm 2 /s, still more preferably 5.5 mm 2 /s to 9.3 mm 2 /s .
• kinematic viscosity of the lubricating oil composition of the present embodiment is preferably from 10.0 mm 2 /s to 40.0 mm 2 /s, more preferably from the viewpoint of improving lubricating performance, viscosity characteristics, and fuel economy. 15.0 mm 2 /s to 38.0 mm 2 /s, more preferably 16.0 mm 2 /s to 30.0 mm 2 /s, still more preferably 17.0 mm 2 /s to 32.0 mm 2 /s, more It is more preferably 18.0 mm 2 /s to 30.0 mm 2 /s.
• the viscosity index of the lubricating oil composition of the present embodiment is preferably 300 or higher, more preferably 320 or higher, even more preferably 350 or higher.
• the dynamic viscosity and viscosity index of the lubricating oil composition are values measured or calculated according to JIS K2283:2000.
• the HTHS viscosity at 150° C. of the lubricating oil composition of the present embodiment is preferably 2.8 mPa s or less, more preferably 1.7 mPa s to 2.8 mPa s, still more preferably 1.8 mPa s to 2.
• the HTHS viscosity at 150° C. of the lubricating oil composition is a value obtained by measuring the viscosity after shearing at a temperature of 150° C. and a shear rate of 10 6 /s according to ASTM D4741.
• the polymer composition of the present embodiment has an excellent effect of improving the viscosity index and has an effect of reducing the HTHS viscosity in the effective temperature range (80° C.). Therefore, the lubricating oil composition containing the polymer composition of the present embodiment, for example, gear oil (manual transmission oil, differential oil, etc.), automatic transmission oil (automatic transmission oil, etc.), continuously variable transmission oil (belt CVT oil , toroidal CVT oil, etc.), drive system oils such as power steering oil, shock absorber oil, and electric motor oil; oil for internal combustion engines (engines) such as gasoline engine, diesel engine, and gas engine oil; hydraulic oil Turbine oil; Compressor oil; Fluid bearing oil; Rolling bearing oil; Refrigerating machine oil; It can be suitably used as a lubricating oil.
• gear oil manual transmission oil, differential oil, etc.
• automatic transmission oil automatic transmission oil, etc.
• continuously variable transmission oil belt CVT oil , toroidal CVT oil, etc.
• drive system oils such as power steering oil
• a lubricating oil composition used in a wider temperature range for example, automobiles such as two-wheeled vehicles and four-wheeled vehicles, trains, ships, and transportation equipment such as airplanes , generators, gears mounted on various machine tools, etc., automatic transmissions, continuously variable transmissions, shock absorbers, power steering, lubricating oil for drive system equipment such as electric motors; gasoline engines, diesel engines, gas engines, etc. lubricating oil for internal combustion engines; can be more preferably used as.
• the lubricating method using the lubricating oil composition containing the polymer composition of the present embodiment preferably includes applying the lubricating oil composition to the apparatus used in each of the applications described above.
• a method of filling and lubricating between each part related to each device can be mentioned.
• the lubricating oil composition for example, automobiles such as two-wheeled vehicles and four-wheeled vehicles, trains, ships, and transportation equipment such as airplanes, generators, Gears mounted on various machine tools, automatic transmissions, continuously variable transmissions, shock absorbers, power steering, drive system equipment such as electric motors; internal combustion engines such as gasoline engines, diesel engines, gas engines; etc. and a method of lubricating between parts related to the drive train equipment or between parts related to the internal combustion engine.
• Drive system equipment using lubricating oil composition Another embodiment includes a drive system device using the lubricating oil composition, preferably a drive system device using the lubricating oil composition as a drive system oil.
• the drive system equipment include automobiles such as two-wheeled vehicles and four-wheeled vehicles, transportation equipment such as trains, ships, and airplanes, generators, and gears mounted on various machine tools, automatic transmissions, and continuously variable transmissions. machine, shock absorber, power steering, electric motor, etc.
• An internal combustion engine using lubricating oil composition includes an internal combustion engine using the lubricating oil composition, preferably an internal combustion engine (engine) using the lubricating oil composition as an engine oil.
• the internal combustion engine include a gasoline engine, a diesel engine, a gas engine, and the like mounted on automobiles such as two-wheeled vehicles and four-wheeled vehicles, trains, ships, and transportation equipment such as airplanes.
• [1] Containing a comb-shaped polymer (X) containing the following structural units (a) to (c) and a heteroatom-containing base oil (Y), Structural unit (a): a structural unit derived from a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms Structural unit (b): a long chain having 6 to 32 carbon atoms A structural unit derived from a long-chain alkyl (meth)acrylate (B) having a chain alkyl group, a structural unit (c): a structural unit derived from a macromonomer (C).
• Structural unit (a) a structural unit derived from a short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms
• Structural unit (b) a long chain having 6 to 32 carbon atoms
• the polymer composition Based on all structural units of the polymer (X), it is 70% by mass or more, The polymer composition, wherein the heteroatom-containing base oil (Y) has a kinematic viscosity at 40° C. of 25 mm 2 /s or less.
• the comb-shaped polymer (X) is a copolymer obtained by polymerization in a polymerization solvent containing a heteroatom-containing base oil (Y).
• the comb polymer (X) has a mass average molecular weight of 100,000 to 900,000.
• a method for producing the polymer composition according to [1] above A short-chain alkyl (meth)acrylate (A) having a short-chain alkyl group having 1 to 5 carbon atoms, a long-chain alkyl (meth)acrylate (B) having a long-chain alkyl group having 6 to 32 carbon atoms, a step (S1) of polymerizing a macromonomer (C) to produce a comb-shaped polymer (X); a step (S2) of dissolving the comb polymer (X) in the heteroatom-containing base oil (Y),
• the blending amount of the short-chain alkyl (meth)acrylate (A) is such that the short-chain alkyl (meth)acrylate (A), the long-chain alkyl (meth)acrylate (B), and the macro Based on the total amount of the monomer (C), it is 70% by mass or more,
• Mass average molecular weight (Mw), molecular weight distribution (Mw/Mn) “1515 isocratic HPLC pump” manufactured by Waters, "2414 refractive index (RI) detector", one column “TSKguardcolumn SuperHZ-L” manufactured by Tosoh Corporation, and two “TSK Super Multipore HZ-M” This was installed in this order from the upstream side, measurement temperature: 40° C., mobile phase: tetrahydrofuran, flow rate: 0.35 mL/min, sample concentration: 1.0 mg/mL, and calculated in terms of standard polystyrene.
• n-butyl methacrylate may be abbreviated as "nC4-MA”.
• n-dodecyl methacrylate a mixture of n-dodecyl methacrylate and n-tridecyl methacrylate manufactured by Kyoeisha Chemical Co., Ltd., product name “Light Ester L-7”
• R b1 is a methyl group
• R b3 is an n-dodecyl group (straight-chain alkyl group having 12 carbon atoms)
• a mixture of n-dodecyl methacrylate and n-tridecyl methacrylate may be abbreviated as "C1213-MA”.
• Macromonomer (C) As the macromonomer (C), one-end methacrylated hydrogenated polybutadiene (Kraton Liquid (registered trademark) L-1253, manufactured by Kuraray Co., Ltd.) having a structural unit derived from one-end methacrylated hydrogenated butadiene was used. .
• the weight average molecular weight is about 7,000 and the number average molecular weight is about 6,800.
• Base oil H1 Trimethylolpropane ester NOF Corporation, product name “Unistar (registered trademark) H-334R” It is a mixed triester of trimethylolpropane with lauric and stearic acids.
• Preparation Example 1 Preparation of lubricating oil composition (E1) containing polymer composition (VME1)
• the polymer composition (VME1) was added and mixed with the base oil A as the lubricating base oil at the ratio shown in Table 1 so that the HTHS viscosity of the lubricating oil composition at 150 ° C. was 2.6 mPa s.
• a lubricating oil composition (E1) containing the polymer composition (VME1) was prepared.
• Lubricating oil composition (E2) containing polymer composition (VME2) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E3) containing polymer composition (VME3) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Preparation Example 4 Preparation of lubricating oil composition (E4) containing polymer composition (VME4)
• base oil A and A lubricating oil composition (E4) containing the polymer composition (VME4) was prepared in the same manner as in Preparation Example 1 using a mixed base oil of base oil H2.
• Lubricating oil composition (C1) containing polymer composition (VME4) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E5) containing polymer composition (VME5) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E6) containing polymer composition (VME6) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E7) containing polymer composition (VME7) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (C2) containing polymer composition (VMC2) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E8) containing polymer composition (VME8) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E9) containing polymer composition (VME9) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Lubricating oil composition (E10) containing polymer composition (VME10) was prepared in the same manner as in Preparation Example 1 except that base oil A was used as the lubricating base oil.
• Table 1 shows the following. It can be seen that the lubricating oil compositions E1 to E4 of Examples 1 to 4 have a higher viscosity index and a lower HTHS viscosity at 80° C. than the lubricating oil composition C1 of Comparative Example 1.
• Table 2 shows the following. It can be seen that the lubricating oil compositions E5 to E7 of Examples 5 to 7 have a higher viscosity index and a lower HTHS viscosity at 80° C. than the lubricating oil composition C2 of Comparative Example 2.
• Table 3 shows the following. It can be seen that the lubricating oil compositions E8 to E10 of Examples 8 to 10 all have a high viscosity index and a low HTHS viscosity at 80°C.

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• 2022
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