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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F220/14—Methyl esters, e.g. methyl (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
  • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (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
  • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • 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
  • C10N2020/04—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
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to a polymer used in engine oil and the like, a friction reducing agent for lubricating oil, and a lubricating oil composition.
• Lubricant oils such as automobile engine oils and drive system oils, contain various friction-reducing agents for the purpose of reducing energy loss due to friction and extending the life of equipment by preventing seizure.
• Friction reducing agents include oiliness improvers such as long-chain fatty acid esters and fatty acid amides, anti-wear agents such as phosphoric acid esters and zinc dithiophosphate, extreme pressure agents such as organic sulfur compounds and organic halogen compounds, organic molybdenum compounds, etc.
• Patent Document 1 describes a repeating unit derived from a polyolefin-based macromonomer and a repeating unit derived from a low molecular weight monomer. It is disclosed that comb-shaped polymers containing units can be suitably used as friction modifiers (friction modifiers). Further, Patent Document 2 discloses that a (meth)acrylic graft copolymer can be suitably used as a friction modifier.
• Patent Documents 1 and 2 are insufficient in reducing friction.
• An object of the present invention is to provide a polymer, which can be used to provide a polymeric lubricating oil additive, a friction reducing agent for lubricating oil, and a lubricating oil composition that have a high friction-reducing effect.
• the purpose is to provide a polymer.
• the side chain polymer structure contains a structural unit derived from an alkyl (meth)acrylate (a) in which the alkyl group has 11 to 30 carbon atoms,
• R 1 is a hydrogen atom or a methyl group
• R 2 represents a hydrogen atom or an organic group containing a polar group.
• the organic group containing a polar group does not contain an alkoxyalkyl group.
• the main chain polymer structure according to any one of [1] to [4], wherein the main chain polymer structure includes a structural unit derived from an alkyl (meth)acrylate (a) in which the alkyl group has 11 to 30 carbon atoms. Polymer.
• the proportion of the main chain polymer structure is preferably 25 to 98% by mass, more preferably 30 to 95% by mass, and even more preferably 40 to 90% by mass, based on the total mass of the polymer.
• the proportion of the side chain polymer structure is preferably 2 to 75% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, based on the total mass of the polymer.
• the alkyl (meth)acrylate (a) is preferably a linear or branched alkyl (meth)acrylate having 11 to 20 carbon atoms; Alkyl methacrylates are more preferred, linear or branched alkyl methacrylates having 11 to 18 carbon atoms are even more preferred, and linear or branched alkyl methacrylates having 12 to 14 carbon atoms are particularly preferred, [1] The copolymer according to any one of [7].
• the content of the structural unit derived from the alkyl (meth)acrylate (a) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 80 to 100% by mass, based on the total mass of the side chain polymer structure.
• the content of the structural unit derived from the alkyl (meth)acrylate (a) is preferably 20 to 90% by mass, more preferably 25 to 85% by mass, and 30 to 80% by mass, based on the total mass of the polymer.
• the polar group of the (meth)acrylate (b) is a hydroxyl group, a carboxy group, an aliphatic heterocycle having 2 to 6 carbon atoms, an aromatic heterocycle having 4 to 10 carbon atoms, an alkoxysilyl group, or a carbon number A 3-9 trialkoxysilyl group, a phosphoric acid group, a phosphoric ester group, an amino group, or an amide group is preferred; a hydroxyl group, a carboxy group, an amino group, or an amide group is more preferred; a hydroxyl group is even more preferred, [ 1] to [10].
• the total number of carbon atoms in the (meth)acrylate (b) is preferably 3 to 10, more preferably 3 to 9, and even more preferably 3 to 8.
• the polymer according to any one of [1] to [11].
• the content of the structural unit derived from the (meth)acrylate (b) is preferably 0.01% by mass or more and 20% by mass or less, and 0.05% by mass or more and 15% by mass, based on the total mass of the polymer. % or less, more preferably 0.1% by mass or more and 5% by mass or less, particularly preferably 0.5% by mass or more and 3% by mass or less. Polymer.
• the alkyl group contains a structural unit derived from an alkyl (meth)acrylate (c) having 1 to 10 carbon atoms
• the alkyl (meth)acrylate (c) is an alkyl (meth)acrylate (c) having an alkyl group having 1 to 4 carbon atoms.
• the polymer according to item 1. [17] A structural unit derived from the alkyl (meth)acrylate (a), a structural unit derived from the (meth)acrylate (b) represented by the general formula (1), and an alkyl group having 1 to 10 carbon atoms.
• the total content of structural units derived from (meth)acrylate (c) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total mass of the polymer,
• the main chain polymer structure includes constitutional units derived from the vinyl radically polymerizable monomer (m1), and at least a portion of the constitutional units derived from the vinyl radically polymerizable monomer (m1) are A structural unit derived from the (meth)acrylate (b), The polymer according to any one of [1] to [17].
• X 1 to X n-1 each independently represent a hydrogen atom, a methyl group, or CH 2 OH
• Y 1 to Y n each independently represent a monomer of the macromonomer (M).
• M macromonomer
• Z represents a terminal group, and n is an integer from 2 to 10,000. represent.
• the vinyl radically polymerizable monomer (m1) is a (meth)acrylate (b) represented by the general formula (1) and an alkyl (meth)acrylate in which the alkyl group has 1 to 10 carbon atoms.
• the content of the structural unit derived from the alkyl (meth)acrylate (a) is preferably 80 to 100% by mass, and 85 to 99.9% by mass, based on the total mass of the macromonomer (M). %, more preferably 90 to 99.8% by mass, and particularly preferably 95 to 99.5% by mass, described in any one of [19] to [23]. polymer.
• the content of structural units derived from alkyl (meth)acrylate (c) in which the alkyl group has 1 to 10 carbon atoms is more than 0% by mass and 20% by mass or less, based on the total mass of the macromonomer (M). [19 ] to [24]. [26] [Content of structural units derived from alkyl (meth)acrylate (c) whose alkyl group has 1 to 10 carbon atoms]/[Content of structural units derived from the alkyl (meth)acrylate (a)] The ratio expressed is preferably 0.001 to 3.5, more preferably 0.002 to 3.0, and even more preferably 0.005 to 2.6, any one of [18] to [25]. Polymers described in.
• the content of the structural unit derived from the macromonomer (M) is preferably 1 to 70% by mass, more preferably 2 to 60% by mass, and further preferably 5 to 50% by mass, based on the total mass of the polymer. Preferred polymer according to any one of [19] to [26].
• the mass average molecular weight (Mw) of the macromonomer (M) measured by gel permeation chromatography is preferably from 2,000 to 100,000, more preferably from 3,000 to 80,000, even more preferably from 4,000 to 50,000, particularly preferably from 5,000 to 30,000. Preferred polymer according to any one of [19] to [27].
• the number average molecular weight (Mn) of the macromonomer (M) measured by gel permeation chromatography (GPC) is preferably 500 to 30,000, more preferably 1,000 to 25,000, even more preferably 2,000 to 20,000, and even more preferably 3,000 to 30,000. 16,000 is particularly preferred, the polymer according to any one of [19] to [28].
• the molecular weight distribution (Mw/Mn) of the macromonomer (M) measured by gel permeation chromatography is preferably 1.0 to 5.0, more preferably 1.3 to 3.0, and 1.5.
• the mass average molecular weight (Mw) of the polymer measured by GPC is preferably 10,000 or more and 500,000 or less, more preferably 15,000 or more and 300,000 or less, and even more preferably 20,000 or more and 200,000 or less. ] to [30].
• the number average molecular weight (Mn) of the polymer measured by gel permeation chromatography (GPC) is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 80,000 or less, and 15,000 or more and 50,000 or less. is more preferred, the polymer according to any one of [1] to [31].
• the molecular weight distribution (Mw/Mn) of the polymer measured by gel permeation chromatography (GPC) is preferably 1.0 or more and 15 or less, more preferably 2.0 or more and 10 or less, and 3.
• a base oil solution containing 2% by mass of the polymer is prepared, and the friction coefficient measured at 40°C using an SRV5 tester (manufactured by Optimol Instruments Pruftechnik GmbH) is preferably 0.16 or less, and 0.
• the polymer according to any one of [1] to [33] more preferably 0.155 or less, and even more preferably 0.15 or less.
• a lubricating oil additive comprising the polymer according to any one of [1] to [34].
• a friction reducing agent for lubricating oil comprising the polymer according to any one of [1] to [34] and a solvent.
• the friction reducing agent for lubricating oil according to [36] wherein the solvent is a base oil.
• the content of the polymer is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and 20 to 60% by mass when the total mass of the lubricating oil additive is 100% by mass. More preferably, the friction reducing agent for lubricating oil according to any one of [36] to [38].
• a lubricating oil composition comprising the friction reducing agent for lubricating oil according to any one of [36] to [39].
• the content of the friction reducing agent for lubricating oil is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, when the total mass of the lubricating oil composition is 100% by mass.
• [42] Use of the polymer according to any one of [1] to [34] for producing a lubricating oil composition.
• [43] Use of the polymer according to any one of [1] to [34] for reducing friction.
• [44] Use of the polymer according to any one of [1] to [34] for improving lubricity.
• [46] Use of a composition comprising the polymer according to any one of [1] to [34] for improving lubricity.
• the solvent is a base oil.
• the base oil is an API standard Group III base oil, an API standard Group III plus base oil, or an API standard Group IV base oil.
• the content of the polymer is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and 0.1 to 25% by mass, when the total mass of the composition is 100% by mass.
• a friction reducer for lubricating oil containing a (meth)acrylic graft copolymer A having a main chain polymer structure and a side chain polymer structure is a (meth)acrylate (b) which contains a structural unit derived from an alkyl (meth)acrylate (a) in which the alkyl group has 11 to 30 carbon atoms in the side chain polymer structure and is represented by the following general formula (1).
• R 1 is a hydrogen atom or a methyl group
• R 2 represents a hydrogen atom or an organic group containing a polar group.
• the organic group containing a polar group does not contain an alkoxyalkyl group.
• [2] The friction reducing agent for lubricating oil according to [1], wherein the polar group of the (meth)acrylate (b) is a hydroxyl group, a carboxy group, an amino group, or an amide group.
• the friction reducing agent for lubricating oil according to [1] wherein the polar group of the (meth)acrylate (b) is a hydroxyl group.
• the (meth)acrylic graft copolymer A of [1] to [3] further contains a structural unit derived from an alkyl (meth)acrylate (c) in which the alkyl group has 1 to 10 carbon atoms.
• the friction reducing agent for lubricating oil according to any one of the above.
• the (meth)acrylic graft copolymer A contains a structural unit derived from an alkyl (meth)acrylate (a) in which the alkyl group has 11 to 30 carbon atoms in the main chain polymer structure [1] - [4] The friction reducing agent for lubricating oil according to any one of [4].
• the (meth)acrylic graft copolymer A contains a structural unit derived from a vinyl radically polymerizable monomer (m1) and a structural unit derived from a macromonomer (M) [1] The friction reducing agent for lubricating oil according to any one of [5]. [7] The friction reducing agent for lubricating oil according to [6], wherein the macromonomer (M) contains a structural unit derived from an alkyl (meth)acrylate (a) in which the alkyl group has 11 to 30 carbon atoms. [8] The friction reducing agent for lubricating oil according to [6], wherein the macromonomer (M) has a structure represented by the following formula (2).
• X 1 to X n-1 each independently represent a hydrogen atom, a methyl group, or CH 2 OH
• Y 1 to Y n each independently represent a monomer of the macromonomer (M).
• M macromonomer
• Z represents a terminal group, and n is an integer from 2 to 10,000. represent.
• the polymer of the present invention it is possible to provide a lubricating oil additive, a friction reducing agent for lubricating oil, and a lubricating oil composition that have a high friction-reducing effect.
• (meth)acrylic is a general term for “acrylic” and “methacrylic”.
• (Meth)acrylate is a generic term for “acrylate” and “methacrylate.”
• "Macromonomer” means a polymer having a radically polymerizable group or an addition-reactive functional group.
• "Vinyl-based radically polymerizable monomer means a monomer having an ethylenically unsaturated bond that is not a macromonomer.
• the polymer of the present invention has a main chain polymer structure and a side chain polymer structure, and the side chain polymer structure is derived from an alkyl (meth)acrylate (a) in which the alkyl group has 11 to 30 carbon atoms. At least one of the main chain polymer structure and side chain polymer structure includes a structural unit derived from (meth)acrylate (b) represented by the following general formula (1).
• R 1 is a hydrogen atom or a methyl group
• R 2 represents a hydrogen atom or an organic group containing a polar group.
• the organic group containing a polar group does not contain an alkoxyalkyl group. .
• Friction modifiers for lubricating oils include polymers.
• the polymer refers to a copolymer in which at least some of the structural units are structural units derived from (meth)acrylic monomers.
• the polymer may further contain a structural unit derived from a monomer other than the (meth)acrylic monomer (for example, styrene, etc.).
• the polymer is preferably a graft copolymer composed of a main chain polymer structure and a side chain polymer structure (branch polymer structure) chemically bonded to the main chain polymer structure (stem polymer structure).
• a graft copolymer is a polymer having one or more blocks connected to a main chain polymer structure as a side chain polymer structure.
• the structures of the main chain polymer and the side chain polymer may be different or the same.
• the method for producing the graft copolymer is not particularly limited, but includes a method in which a macromonomer having a radically polymerizable double bond at the end is produced as a side chain polymer structure, and then radically polymerized with a monomer that becomes a constituent unit of the main chain polymer.
• the polymer has a side chain polymer structure containing a constitutional unit derived from an alkyl (meth)acrylate (a) (hereinafter also referred to as “component (a)”) in which the alkyl group has 11 to 30 carbon atoms, and A graft copolymer containing a structural unit derived from (meth)acrylate (b) (hereinafter also referred to as “component (b)”) represented by general formula (1) is preferable.
• Component (a) is preferably a linear or branched alkyl (meth)acrylate having 11 to 20 carbon atoms, since it has excellent solubility in base oil and a friction reducing effect.
• Chain or branched alkyl methacrylates are more preferred, straight chain or branched alkyl methacrylates having 11 to 18 carbon atoms are even more preferred, and straight chain or branched alkyl methacrylates having 12 to 14 carbon atoms are particularly preferred. preferable.
• solubility in base oil and friction reduction performance it is possible to improve solubility in base oil and friction reduction performance, and improve fuel efficiency by lowering the viscosity of the lubricating oil composition. It is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the structure.
• solubility in base oil and friction reduction performance it is possible to improve solubility in base oil and friction reduction performance, and improve fuel efficiency by lowering the viscosity of the lubricating oil composition. It is preferably 20 to 90% by weight, more preferably 25 to 85% by weight, and even more preferably 30 to 80% by weight based on the total weight. Since the solubility of the polymer in base oil can be improved, it is preferable that the polymer also contains a structural unit derived from the component (a) as a structural unit in the main chain polymer structure.
• the component (b) is a (meth)acrylate represented by the following general formula (1) (hereinafter, the (meth)acrylate (b) represented by the following general formula (1) is referred to as a "polar group-containing (meth)acrylate”). (Also referred to as acrylate (b).)
• R 1 is a hydrogen atom or a methyl group
• R 2 represents a hydrogen atom or an organic group containing a polar group.
• the organic group containing a polar group does not contain an alkoxyalkyl group.
• polar groups include hydroxyl groups, carboxy groups, heterocyclic structures (e.g., aliphatic heterocycles having 2 to 6 carbon atoms, aromatic heterocycles having 4 to 10 carbon atoms), alkoxysilyl groups, and 3 to 3 carbon atoms. Examples include a trialkoxysilyl group of No.
• an amino group for example, a secondary amino group such as a dimethylamino group and a diethylamino group
• an amide group for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylates with hydroxyl groups such as (meth)acrylate, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate; (meth)acrylic acid, succinic acid 2-(meth)acrylate; ) (Meth)acrylates containing a carboxy group such as acrylo
• (Meth)acrylates having a heterocyclic structure such as tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane (meth)acrylates having a trialkoxysilyl group having 3 to 9 carbon atoms;
• (meth)acrylates having a phosphate ester group such as 2-(meth)acryloyloxyethyl acid phosphate; dimethylaminoethyl (meth)acrylate , (meth)acrylates having an amino group such as diethylaminoethyl (meth)acrylate;
• (meth)acrylates having an amide group such as (meth)acrylamide, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, and the like.
• the polar group-containing (meth)acrylate (b) is preferably a (meth)acrylate having a hydroxyl group or a carboxy group, more preferably a (meth)acrylate having a hydroxyl group or a carboxy group, and a (meth)acrylate having a hydroxyl group is more preferable.
• Acrylates are more preferred, and acrylates having hydroxyl groups are particularly preferred.
• the total carbon number of the polar group-containing (meth)acrylate (b) is preferably 3 to 10, more preferably 3 to 9, and even more preferably 3 to 8.
• organic groups having a polar group it is more preferable to use a highly polar group.
• a hydroxyl group, a carboxy group, an amino group, an amide group, a phosphoric acid group, and a phosphate ester group have greater polarity than an alkoxyalkyl group and are preferred polar groups.
• polymers improve their affinity with metal surfaces through the action of intermolecular forces such as van der Waals forces and hydrogen bonds, and the formation of chemical bonds such as covalent bonds and ionic bonds. can be done. As a result, the adhesion of the polymer to the metal surface is improved, and the friction reduction performance can be improved.
• the content of the structural unit is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.05% by mass or more and 15% by mass or less, even more preferably 0.1% by mass or more and 5% by mass or less, and 0.01% by mass or more and 15% by mass or less. Particularly preferably 5% by mass or more and 3% by mass or less.
• the above-mentioned polymer is further composed of an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms as a structural unit.
• (c) (hereinafter also referred to as "component (c)" is preferably contained.
• component (c) for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl ( (meth)acrylates having a linear alkyl group such as meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, n-nonyl(meth)acrylate; i-propyl(meth)acrylate; Branches such as i-butyl (meth)acrylate, t-butyl (meth)acrylate, i-nonyl (meth)acrylate, n-decyl (meth)acrylate, i-decyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.
• (Meth)acrylates having an alkyl group of Examples include (meth)acrylates having a cyclic alkyl group. Two or more of these may be used in combination. Because of their excellent friction-reducing effect, alkyl (meth)acrylates having 1 to 4 carbon atoms are preferred, alkyl acrylates having 1 to 4 carbon atoms are more preferred, and n-butyl acrylate is even more preferred. Since the friction reducing effect is excellent, the structural unit derived from the component (c) is preferably contained in the main chain polymer structure.
• the content of the structural unit is preferably 20% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 90% by mass or less, and even more preferably 45% by mass or more and 80% by mass or less.
• the total amount of the structural units derived from the components (a) to (c) is preferably 70% by mass or more, and 80% by mass, based on the total mass of the polymer. It is more preferably at least 90% by mass, and even more preferably at least 90% by mass. The total amount of the structural units derived from the components (a) to (c) does not exceed 100% by mass based on the total mass of the polymer.
• the polymer may contain structural units derived from other radically polymerizable vinyl compounds (d) (hereinafter also referred to as "component (d)”) other than the components (a) to (c).
• component (d) includes, for example, styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene, vinyl acetate, and (meth)acrylates other than components (a) to (c).
• (meth)acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate.
• the polymer may contain structural units derived from the components (a) to (d) above in
• the polymer contains a structural unit derived from a vinyl radically polymerizable monomer (m1) (hereinafter also referred to as “component (m1)”) and a macromonomer (M) (hereinafter also referred to as “component (M)”).
• component (m1) vinyl radically polymerizable monomer
• M macromonomer
• ) may also include a structural unit derived from Component (M) contains a structural unit derived from a monomer (m2) having a vinyl radically polymerizable group.
• Examples of the component (m1) include styrene, vinyl acetate, (meth)acrylate compounds, and the like.
• Examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl ( meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, n-nonyl(meth)acrylate, n-decyl(meth)acrylate, n-undecyl(meth)acrylate, n-dodecyl(meth)acrylate Straight chain alkyl groups such as acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-cety
• (meth)acrylate i-propyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, s-butyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Acrylate, i-nonyl (meth)acrylate, i-decyl (meth)acrylate, 3-i-propylheptyl (meth)acrylate, i-undecyl (meth)acrylate, 2-t-butylheptyl (meth)acrylate, i- (Meth)acrylates having a branched alkyl group such as dodecyl (meth)acrylate, i-tridecyl (meth)acrylate, i-tetradecyl (meth)acrylate, and i-behenyl (meth)acrylate; cyclopentyl (meth
• (meth)acrylates having a heterocyclic structure such as tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, (meth)acryleoylmorpholine; methoxyethyl (meth)acrylate, ethoxyethyl ( Alkoxy(meth)acrylates such as meth)acrylate, butoxyethyl(meth)acrylate; allyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, 3-(meth)acryloxypropyl Trimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate, trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, dimethylaminoethyl (meth
• component (m1) contains two or more structural units derived from a monomer (m2) having a vinyl radically polymerizable group (hereinafter also referred to as "component (m2)"), and has a radically polymerizable group at the end. It is a compound having the above-mentioned (a) component as the (m2) component. Examples of the (m2) component other than the (a) component include the compounds listed above as the (m1) component.
• the structural unit derived from the component (a) be contained in an amount of 50% by mass or more, and preferably 60% by mass or more based on the total mass of the component (M). It is more preferable to contain 70% by mass or more, and it is particularly preferable to contain 80% by mass or more.
• the structural unit derived from component (a) may be 100% by mass, and preferably less than 100% by mass, with respect to the total mass of component (M).
• the structural unit derived from the component (c) be contained in an amount of more than 0% by mass and not more than 20% by mass, based on the total mass of the component (M). It is more preferable to contain .1 to 15% by weight, even more preferably to contain 0.2 to 10% by weight, and particularly preferably to contain 0.5 to 5% by weight.
• the ratio expressed by [content of structural units derived from component (c)]/[content of structural units derived from component (a)] is as follows: It is preferably from 0.001 to 3.5, more preferably from 0.002 to 3.0, even more preferably from 0.005 to 2.6.
• the component (M) preferably has a structure represented by the following formula (2).
• X 1 to X n-1 each independently represent a hydrogen atom, a methyl group, or CH 2 OH
• Y 1 to Y n each independently represent a monomer constituent unit (m2)
• Z represents a terminal group
• n represents an integer from 2 to 10,000.
• X 1 to X n-1 and Y 1 to Y n are each independently substituents bonded to the vinyl group of component (m2).
• Y 1 to Y n represent, for example, OR 1 , a halogen atom, COR 2 , COOR 3 , CN, CONR 4 R 5 , NHCOR 6 , or R 7 , and R 1 to R 7 each independently represent a hydrogen atom, Indicates an alkyl group, an aryl group, a heteroaryl group, etc.
• the terminal group Z includes a group derived from a hydrogen atom and a radical polymerization initiator, similar to the terminal group of a polymer obtained by known radical polymerization.
• the content of the structural units derived from the component (M) should be 1 to 1 with respect to the total mass of the polymer. It is preferably 70% by weight, more preferably 2 to 60% by weight, and even more preferably 5 to 50% by weight.
• the mass average molecular weight of the macromonomer (M) measured by gel permeation chromatography is because it can improve solubility in base oil and friction reduction performance, and improve fuel efficiency by lowering the viscosity of the lubricating oil composition.
• Mw is preferably 2,000 to 100,000, more preferably 3,000 to 80,000, even more preferably 4,000 to 50,000, particularly preferably 5,000 to 30,000.
• the macromonomer (M) was measured by gel permeation chromatography (GPC) because it can improve solubility in base oil and friction reduction performance, and improve fuel efficiency by lowering the viscosity of the lubricating oil composition.
• the number average molecular weight (Mn) is preferably 500 to 30,000, more preferably 1,000 to 25,000, even more preferably 2,000 to 20,000, and particularly preferably 3,000 to 16,000.
• Mw/Mn is preferably 1.0 to 5.0, more preferably 1.3 to 3.0, even more preferably 1.5 to 2.5.
• the component (M) may be produced by a known method or may be commercially available.
• Examples of the method for producing component (M) include a method using a cobalt chain transfer agent (US Pat. No. 4,680,352), a method using an ⁇ -substituted unsaturated compound such as ⁇ -bromomethylstyrene as a chain transfer agent. method (WO 88/04304), method of chemically bonding polymerizable groups (JP 60-133007 and US Pat. No. 5,147,952), and thermal decomposition method (JP 11-240854) (Government).
• a method of manufacturing using a cobalt chain transfer agent is preferable because it requires fewer manufacturing steps and uses a catalyst with a high chain transfer constant. Since the cobalt chain transfer agent has a high chain transfer constant, a macromonomer with a controlled molecular weight can be obtained by adding a small amount.
• cobalt chain transfer agent known cobalt complexes can be used.
• the amount of the cobalt chain transfer agent is preferably 0.00001 to 0.1 part by mass, more preferably 0.00005 to 0.05 part by mass, based on 100 parts by mass of the component (m2). Particularly preferred is 0.0001 to 0.02 parts by mass.
• the mass average molecular weight (Mw) measured by GPC of the polymer contained in the friction reducing agent for lubricating oil of the present invention can provide good solubility in base oil and good friction reducing performance, and can improve the solubility and friction reducing performance of the lubricating oil composition. Since fuel efficiency can be improved by increasing the viscosity, it is preferably 10,000 or more and 500,000 or less, more preferably 15,000 or more and 300,000 or less, and even more preferably 20,000 or more and 200,000 or less.
• the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of Polymer A contained in the friction reducing agent for lubricating oils of the present invention can provide good solubility in base oil and friction reducing performance. Since fuel efficiency can be improved by lowering the viscosity of the lubricating oil composition, it is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 80,000 or less, and even more preferably 15,000 or more and 50,000 or less.
• the molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) of Polymer A contained in the friction reducing agent for lubricating oils of the present invention indicates that it has good solubility in base oil and friction reducing performance. 1.0 or more and 15 or less, more preferably 2.0 or more and 10 or less, and 3.0 or more and 8.0 or less, since fuel efficiency can be improved by lowering the viscosity of the lubricating oil composition. It is even more preferable that there be.
• the friction reducing agent for lubricating oil of the present invention contains the alkyl (meth)acrylate (a) to (c) components, the other radically polymerizable vinyl compound (d) component, and the macromonomer (M) component in the base oil. It can be produced by polymerizing a monomer mixture containing the following using a known method.
• the base oil is not particularly limited, but includes API standard Group III base oils such as YUBASE3 manufactured by SK Lubricants, API Group III plus base oils such as YUBASE4 manufactured by SK Lubricants, and API standard Group IV base oils such as polyalphaolefin. etc.
• the polymerization may be carried out under known conditions, it is preferable to use ⁇ -methylstyrene dimer as the chain transfer agent because it has a particularly excellent effect of suppressing heat generation during polymerization.
• the friction reducing agent for lubricating oils containing the polymer of the present invention is suitable for use in engine oils, drive system oils (gear oils, transmission oils), hydraulic oils, etc. used in mobility such as automobiles and ships, industrial machinery, robots, etc. It can be used as a friction reducer added to lubricating oils such as metal working oils.
• Base oils for the engine oil, gear oil, hydraulic oil, etc. include mineral base oils refined from crude oil and chemically synthesized synthetic oils, such as API standard Group III oils such as YUBASE3 manufactured by SK Lubricants. , base oils of API standard Group III plus such as YUBASE4 manufactured by SK Lubricants, and base oils of API standard Group IV such as polyalphaolefin.
• the lubricating oil composition of the present invention is one in which the friction reducing agent for lubricating oil of the present invention is blended with a base oil.
• the lubricating oil composition of the present invention may contain other additives other than the lubricating oil friction reducing agent of the present invention.
• Other additives include antioxidants, viscosity index improvers, pour point depressants, detergent dispersants, corrosion inhibitors, rust inhibitors, antifoaming agents, emulsifiers, fungicides, demulsifiers, and the like.
• friction reducing agents other than those of the present invention include oiliness improvers such as long-chain fatty acid esters and fatty acid amides, anti-wear agents such as phosphoric acid esters and zinc dithiophosphate, and extreme pressure agents such as organic sulfur compounds and organic halogen compounds. , a friction modifier such as an organic molybdenum compound.
• the lubricating oil composition of the present invention may be a grease containing a thickener.
• the thickener include soap-based (lithium soap, calcium soap, sodium soap, aluminum soap, etc.), inorganic-based (bentonite, silica gel, etc.), organic-based (polyurea, polyurethane, etc.), and the like.
• the content of the friction reducing agent for lubricating oil of the present invention contained in the lubricating oil composition is preferably 0.01 to 30% by mass, and 0.01 to 30% by mass, when the total mass of the lubricating oil composition is 100% by mass. More preferably 05 to 25% by mass, and even more preferably 0.1 to 20% by mass.
• a base oil solution containing 2% by mass of the polymer is prepared, and the friction coefficient measured at 40°C using an SRV5 tester (manufactured by Optimol Instruments Pruftechnik GmbH) is preferably 0.16 or less, and 0.155 or less. More preferably, it is 0.15 or less.
• a lubricating oil composition was prepared by mixing the obtained polymer, YUBASE4 and MoDTC (molybdenum dialkyl dithiocarbamate) for 10 minutes while heating to 65°C with the compositions listed in Tables 2 to 6, and a lubricating oil composition was prepared using an SRV5 tester (Optimol The coefficient of friction at 40° C. was measured using an instrument (manufactured by Pruftechnik GmbH). The measurement conditions were as follows, and the friction coefficient was evaluated 30 minutes after the start of the measurement. ⁇ Test method: Ball on disc (ball diameter: 10mm, ball and disc material: SUJ2) ⁇ Test mode: Reciprocating (50Hz, stroke 1mm) ⁇ Load: 200N
• the temperature of the solution was raised to 40° C., and dissolved oxygen was removed by bubbling nitrogen for 2 hours while stirring.
• a mixed solution consisting of YUBASE4 (2 parts) and 0.1 part of t-amylperoxy-2-ethylhexanoate (manufactured by Arkema Yoshitomi, trade name: Luperox 575) as a polymerization initiator was added, and the temperature of the liquid was raised to 90°C. After raising the temperature to .degree. C. and stirring for 2.5 hours, a mixed solution consisting of YUBASE 4 (10 parts) and Luperox 26 (0.7 parts) was added dropwise over 1 hour.
• Example 1 In a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, 50 parts of YUBASE4, 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2, and n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation, trade name :nBA), 18 parts of lauryl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name: LA), 1 part of 4-hydroxybutyl acrylate (manufactured by Mitsubishi Chemical Corporation, trade name: 4HBA), and t as a polymerization initiator.
• nBA n-butyl acrylate
• LA lauryl acrylate
• 4HBA 4-hydroxybutyl acrylate
• a liquid mixture consisting of YUBASE 4 (30 parts) and Perbutyl O (0.5 parts) was added dropwise over 1 hour. Thereafter, the temperature was raised to 110°C and held for 1 hour, and then 41.1 parts of YUBASE4 was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• the polymer composition also includes the structural unit in the macromonomer (M).
• Example 2 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4HBA (3 parts), Luperox 575 (0.1 part), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 3 When preparing a lubricating oil composition using the friction reducing agent for lubricating oil obtained in Example 2, MoDTC was added at the ratio shown in Table 2 and used for evaluation. Table 2 shows the evaluation results of the obtained lubricating oil composition.
• Example 4 In a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, 50 parts of YUBASE4, 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3, 56 parts of nBA, 18 parts of LA, and 4HBA were added. 1 part, 0.03 part of Perbutyl O, and 0.5 part of Nohumer MSD were added, and dissolved oxygen was removed by bubbling nitrogen while stirring. The liquid temperature was raised to 85°C and held for 3.5 hours, and then a mixed solution consisting of YUBASE4 (42 parts) and Perbutyl O (0.015 parts) was added dropwise over 2 hours. Furthermore, after holding the temperature at 85° C.
• a mixed solution consisting of YUBASE4 (30 parts) and Perbutyl O (0.5 parts) was added dropwise over a period of 1 hour. Thereafter, the temperature was raised to 110°C and held for 1 hour, and then 41.1 parts of YUBASE4 was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 5 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4HBA (3 parts), Luperox 575 (0.1 part), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 6 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M3 obtained in Production Example 4 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4HBA (3 parts), Luperox 575 (0.1 part), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 7 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (44 parts), LA (30 parts), 4HBA (1 part), Luperox 575 (0.1 part), Nofumar MSD (0.3 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 8 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and a mixed liquid consisting of YUBASE4 (25 parts), LA (65 parts), 4HBA (10 parts), Luperox 575 (0.1 parts), and Nofumar MSD (0.4 parts) was added. The mixture was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 9 30 parts of YUBASE4 and 9.5 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (69 parts), LA (22 parts), 4HBA (4 parts), Luperox 575 (0.1 part), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110°C and maintaining it for 1 hour, YUBASE4 (76.2 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 2 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 10 30 parts of YUBASE4 and 95.1 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and a mixed solution consisting of YUBASE4 (25 parts), nBA (48 parts), 4HBA (2 parts), Luperox 575 (0.1 part), and Nofumar MSD (0.9 parts) was added. The mixture was added dropwise over 4 hours. After holding at 85° C.
• Example 11 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: HEA) (1 part), and Luperox were added. A mixed solution consisting of 575 (0.1 part) and Nohumer MSD (0.5 part) was added dropwise over 4 hours.
• Example 12 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), HEA (3 parts), Luperox 575 (0.1 part), Nofumar MSD (0.7 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 13 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), HEA (3 parts), Luperox 575 (0.1 part), Nofumar MSD (0.7 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 14 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), glycerin monomethacrylate (manufactured by NOF Corporation, trade name: Bremmer GLM) (1 part), Luperox 575 were added. (0.1 part) and Nohumer MSD (0.4 part) were added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 15 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (18 parts), Blenmar GLM (2 parts), Luperox 575 (0.1 part), Nofmar MSD (0.6 parts) were added. A mixture consisting of parts) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 16 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (18 parts), Blenmar GLM (2 parts), Luperox 575 (0.1 part), Nofmar MSD (0.6 parts) were added. A mixture consisting of parts) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 17 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), acrylic acid (manufactured by Mitsubishi Chemical Corporation, trade name: AA) (1 part), Luperox 575 (0 .1 part) and Nohumer MSD (0.6 part) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 18 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), AA (3 parts), Luperox 575 (0.1 parts), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 19 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), AA (3 parts), Luperox 575 (0.1 part), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 3 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 20 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and a mixed solution consisting of YUBASE4 (25 parts), LA (65 parts), AA (10 parts), Luperox 575 (0.1 parts), and Nofumar MSD (0.9 parts) was added. The mixture was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110°C and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 21 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), diethyl acrylamide (manufactured by KJ Chemicals, trade name: DEAA) (1 part), and Luperox 575 (0 parts) were added. .4 parts) and Nohumer MSD (0.9 parts) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 95° C. and maintaining it for 2 hours, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 22 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (54 parts), LA (16 parts), DEAA (5 parts), Luperox 575 (0.4 parts), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 95° C. and maintaining it for 2 hours, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 23 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (54 parts), LA (16 parts), DEAA (5 parts), Luperox 575 (0.4 parts), Nofumar MSD (0.9 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 95° C. and maintaining it for 2 hours, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 24 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), polypropylene glycol monomethacrylate (manufactured by NOF Corporation, trade name: Blenmar PP-800, propylene oxide average addition) were added.
• Example 25 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (54 parts), LA (16 parts), Blenmar PP-800 (5 parts), Luperox 575 (0.4 parts), Nofumar MSD (0 .9 parts) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 95° C. and maintaining it for 2 hours, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 26 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (54 parts), LA (16 parts), Blenmar PP-800 (5 parts), Luperox 575 (0.4 parts), Nofumar MSD (0 .9 parts) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 95° C. and maintaining it for 2 hours, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 27 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM503) (1 A mixed solution consisting of Luperox 575 (0.1 part), Nofumar MSD (0.7 part) was added dropwise over 4 hours.
• Example 28 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded.
• the liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM503) (3 A mixed solution consisting of 1 part), Luperox 575 (0.1 part), and Nofmar MSD (0.7 part) was added dropwise over 4 hours. After holding at 85° C. for 1 hour, a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C.
• YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent.
• Example 29 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), 4HBA (1 part), Luperox 575 (0.1 part), Nofumar MSD (1.5 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 4 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 30 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4HBA (3 parts), Luperox 575 (0.1 parts), Nofumar MSD (1.5 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 31 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), HEA (1 part), Luperox 575 (0.1 part), Nofumar MSD (1.2 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 32 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), HEA (3 parts), Luperox 575 (0.1 parts), Nofumar MSD (1.5 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 33 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M3 obtained in Production Example 4 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), 4HBA (1 part), Luperox 575 (0.1 part), Nofumar MSD (1.5 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 34 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M3 obtained in Production Example 4 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4HBA (3 parts), Luperox 575 (0.1 parts), Nofumar MSD (1.5 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 35 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M3 obtained in Production Example 4 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), HEA (1 part), Luperox 575 (0.1 part), Nofumar MSD (1.2 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 36 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M3 obtained in Production Example 4 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), HEA (3 parts), Luperox 575 (0.1 parts), Nofumar MSD (1.5 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 5 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 37 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), dimethylaminoethyl acrylate (manufactured by Toagosei Co., Ltd., trade name: Aron DA) (3 parts), Luperox A mixed solution consisting of 575 (0.1 part) and Nohumer MSD (0.5 part) was added dropwise over 4 hours.
• Example 38 30 parts of YUBASE4 and 95.1 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (49 parts), polyethylene glycol monoacrylate (number of moles of ethyleneoxy group added: about 4.5, manufactured by NOF Corporation, product name: AE- 200) (1 part), Luperox 575 (0.1 part), and Nofumer MSD (0.9 part) were added dropwise over 4 hours. After holding at 85° C.
• Example 39 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), polyethylene glycol monoacrylate (number of moles of ethyleneoxy group added: approximately 10, manufactured by NOF Corporation, product) were added. A mixed solution consisting of AE-400 (1 part), Luperox 575 (0.4 part), and Nofmar MSD (0.9 part) was added dropwise over 4 hours.
• Example 40 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), polypropylene glycol monoacrylate (number of moles of propyleneoxy group added: approximately 6, manufactured by NOF Corporation, product) were added. A mixed solution consisting of AP-400 (1 part), Luperox 575 (0.1 part), and Nofmar MSD (0.5 part) was added dropwise over 4 hours.
• Example 41 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M4 obtained in Production Example 5 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (56 parts), LA (18 parts), 4-hydroxybutyl acrylate (1 part), Luperox 575 (0.1 part), Nofumar MSD ( A mixed solution consisting of 0.5 part) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 42 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4-hydroxybutyl acrylate (3 parts), Luperox 575 (3 parts), Nofumar MSD (4 parts) were added. ) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 43 30 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4-hydroxybutyl acrylate (3 parts), Luperox 575 (1 part), Nofumar MSD (1. A mixed solution consisting of 9 parts) was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 44 40 parts of YUBASE4 and 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and a mixture consisting of YUBASE4 (25 parts), nBA (55 parts), LA (17 parts), 4-hydroxybutyl acrylate (3 parts), and Luperox 575 (0.1 part) was prepared. The liquid was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (48.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Example 45 30 parts of YUBASE4 and 95.1 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and from YUBASE4 (25 parts), nBA (47 parts), 4-hydroxybutyl acrylate (3 parts), Luperox 575 (0.1 parts), Nofumer MSD (1.3 parts). A mixed solution was added dropwise over 4 hours. After holding at 85° C.
• Example 46 30 parts of YUBASE4 and 133.1 parts of the YUBASE4 solution of macromonomer M2 obtained in Production Example 3 were added to a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and dissolved oxygen was removed by bubbling nitrogen while stirring. Excluded. The liquid temperature was raised to 85°C, and a mixture consisting of YUBASE4 (30 parts), nBA (27 parts), 4-hydroxybutyl acrylate (3 parts), Luperox 575 (1 part), and Nofumer MSD (0.9 parts) was added. The liquid was added dropwise over 4 hours. After holding at 85° C.
• a mixed solution of YUBASE4 (20 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110°C and maintaining it for 1 hour, YUBASE4 (44.5 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• ⁇ Comparative example 1> In a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, 50 parts of YUBASE4, 47.6 parts of the YUBASE4 solution of macromonomer M1 obtained in Production Example 2, 56 parts of nBA, 19 parts of LA, and Perbutyl O were added. 0.03 part of Nofumer MSD and 0.05 part of Nohumer MSD were added, and dissolved oxygen was removed by bubbling nitrogen while stirring. The liquid temperature was raised to 85° C. and held for 3.5 hours, and then a mixed solution consisting of YUBASE 4 (42 parts) and Perbutyl O (0.015 parts) was added dropwise over 2 hours. Furthermore, after holding the temperature at 85° C.
• a liquid mixture consisting of YUBASE 4 (30 parts) and Perbutyl O (0.5 parts) was added dropwise over 1 hour. Thereafter, the temperature was raised to 110°C and held for 1 hour, and then 41.1 parts of YUBASE4 was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• ⁇ Comparative example 2> In a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, 72.6 parts of YUBASE4, 44 parts of nBA, 30 parts of LA, 24.5 parts of Acryester SL, 0.5 part of MMA, and 1 part of 4HBA were added. 1 part, 0.03 part of Perbutyl O, and 0.15 part of Nohumer MSD were added, and dissolved oxygen was removed by bubbling nitrogen while stirring. The liquid temperature was raised to 85°C and held for 3.5 hours, and then a mixed solution consisting of YUBASE4 (42 parts) and Perbutyl O (0.015 parts) was added dropwise over 2 hours. Furthermore, after holding the temperature at 85° C.
• a liquid mixture consisting of YUBASE4 (60 parts) and Perocta O (0.5 parts) was added dropwise over a period of 1 hour. Thereafter, the temperature was raised to 110° C. and maintained for 1 hour, and then 11.1 parts of YUBASE4 was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• a mixed solution of YUBASE4 (50 parts) and Luperox 575 (0.5 parts) was added dropwise over 1.5 hours. After raising the temperature to 110° C. and maintaining it for 1 hour, YUBASE4 (58.1 parts) was added and cooled to obtain a YUBASE4 solution containing 35% by mass of the polymer.
• Table 6 shows the evaluation results of the lubricating oil composition containing the obtained friction reducing agent for lubricating oil.
• Comparative Example 1 the coefficient of friction was high because the polymer did not contain the structural unit derived from component (b). Moreover, since Comparative Example 2 did not have a side chain polymer structure, the coefficient of friction was high. In Comparative Example 3, the polymer contained a structural unit having an alkoxyalkyl group as a polar group, but did not contain a structural unit derived from component (b), so the friction coefficient was high similarly to Comparative Example 1. Comparative Example 4 had a high coefficient of friction because the side chain polymer structure did not contain the structural unit derived from component (a).
• ⁇ SLMA A mixture of alkyl methacrylate whose alkyl group has 12 carbon atoms and alkyl methacrylate whose alkyl group has 13 carbon atoms (manufactured by Mitsubishi Chemical Corporation, product name: Acryester SL)
• ⁇ MMA Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, product name: Acryester M)
• ⁇ SMA Stearyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Ester S)
• ⁇ EHMA 2-ethylhexyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name "Acryester EH")
• ⁇ M1 Macromonomer synthesized in Production Example 2
• ⁇ M2 Macromonomer synthesized in Production Example 3
• ⁇ M3 Macromonomer synthesized in Production Example 4
• ⁇ M4 Macromonomer
• the polymer of the present invention it is possible to provide a lubricating oil additive, a friction reducing agent for lubricating oil, and a lubricating oil composition that have a high friction-reducing effect.

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• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Lubricants (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2023
  • 2023-09-08 JP JP2024543064A patent/JP7663156B2/ja active Active
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  • 2023-09-08 WO PCT/JP2023/032863 patent/WO2024053735A1/ja not_active Ceased
  • 2023-09-08 EP EP23863273.1A patent/EP4585626A4/en active Pending
• 2024
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• 2025
  • 2025-03-06 US US19/072,754 patent/US20250197547A1/en active Pending

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