Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
  • B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
• • 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
• • 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
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/24—Polyethers
  • C10M145/26—Polyoxyalkylenes
• • 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
  • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
  • C10M155/02—Monomer containing silicon
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/08—Aldehydes; Ketones
  • C10M2207/085—Aldehydes; Ketones 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/18—Anti-foaming property
• • 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
  • C10N2040/14—Electric or magnetic purposes
• • 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
• • 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
  • C10N2040/40—Generators or electric motors in oil or gas winning field

Definitions

• the present invention relates to an antifoaming agent, a lubricating oil composition containing the antifoaming agent, and a machine using the lubricating oil composition.
• foaming increases in low-viscosity lubricating oil, and the foaming reduces the lubrication performance and cooling efficiency; A rise in oil temperature accelerates deterioration of the lubricating oil.
• Lubricating oils with high antifoaming properties are required so that foaming can be suppressed from the beginning of operation over a long period of time.
• Lubricating oils contain antifoaming agents to prevent foaming.
• Polysiloxane-based antifoaming agents are known as such antifoaming agents, and various polysiloxane-based antifoaming agents have been proposed (Patent Documents 1 to 3).
• Lubricating oils are becoming less viscous in order to achieve higher performance and fuel efficiency, and conventional polysiloxane defoaming agents cannot provide sufficient defoaming properties for low-viscosity lubricating oils. was there.
• the problem to be solved by the present invention is to provide an antifoaming agent that exhibits excellent antifoaming properties.
• the present inventors have conducted intensive studies to solve the above problems, and as a result, a polymerizable monomer (1) having a silicone chain-containing functional group and a polymerizable monomer having a polyoxyalkylene chain-containing functional group
• a polymer containing (2) as a polymerization component is an antifoaming agent exhibiting excellent antifoaming properties, and completed the present invention.
• the present invention is a polymer comprising a polymerizable monomer (1) having a functional group containing a silicone chain and a polymerizable monomer (2) having a functional group containing a polyoxyalkylene chain as polymerization components. It relates to antifoaming agents.
• the present invention can provide an antifoaming agent that exhibits excellent antifoaming properties.
• (meth)acrylate refers to one or both of acrylate and methacrylate.
• the antifoaming agent of the present invention is a polymer comprising a polymerizable monomer (1) having a functional group containing a silicone chain and a polymerizable monomer (2) having a functional group containing a polyoxyalkylene chain as polymerization components.
• a polymer containing the polymerizable monomer (1) and the polymerizable monomer (2) as polymerization components may be referred to as "the polymer of the present invention”.
• polymerization component means a component that constitutes a polymer, and does not include solvents, polymerization initiators, etc. that do not constitute a polymer.
• the "polymerizable monomer” means a compound having a polymerizable unsaturated group, and the polymerizable unsaturated groups possessed by the polymerizable monomer (1) and the polymerizable monomer (2)
• Examples include (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, vinyl ether group, allyl group, styryl group, (meth)acryloylamino group, maleimide group and the like.
• a (meth)acryloyl group and a (meth)acryloyloxy group are preferable because of the availability of raw materials and favorable polymerization reactivity.
• silicone chain in the silicone chain-containing functional group possessed by the polymerizable monomer (1) examples include groups represented by the following general formula (SILICONE).
• each R is independently an alkyl group having 1 to 18 carbon atoms or a phenyl group; n1 is the number of repetitions. )
• the alkyl group having 1 to 18 carbon atoms for R may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples thereof include methyl group, ethyl group, normal propyl group, isopropyl group, n- Butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like can be mentioned.
• the alkyl group of 1 to 18 carbon atoms for R is preferably an alkyl group of 1 to 6 carbon atoms, more preferably a methyl group.
• n1 is, for example, an integer in the range of 1-200, preferably an integer in the range of 1-150.
• the number average molecular weight of the silicone chain portion of the silicone chain-containing functional group is, for example, in the range of 100 to 20,000, preferably in the range of 400 to 18,000, more preferably in the range of 1,000 to 15,000. and more preferably in the range of 1,500 to 12,000.
• the polymerizable monomer (1) is preferably one or more selected from the group consisting of compounds represented by the following general formula (1-A) and compounds represented by the following general formula (1-B). be.
• R 1 is a hydrogen atom or a methyl group
• L 1 is a divalent or trivalent organic group or a single bond
• L2 is a divalent organic group or a single bond
• R2 is a functional group containing a silicone chain
• R 3 is a divalent silicone chain-containing functional group
• x is an integer of 1 or 2;
• the divalent organic group of L 1 is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• the alkylene group having 1 to 50 carbon atoms for L 1 includes methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and n-octylene. group, n-nonylene group, n-decylene group, n-dodecylene group, isopropylene group, 2-methylpropylene group, 2-methylhexylene group, tetramethylethylene group, etc.
• the alkylene group having 1 to 50 carbon atoms of L 1 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, still more preferably a methylene group, ethylene group, n-propylene group or isopropylene group.
• the alkyleneoxy group having 1 to 50 carbon atoms in L 1 is, for example, a group in which one or more —CH 2 — in the alkylene group is substituted with —O—.
• the alkyleneoxy group having 1 to 50 carbon atoms of L 1 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and still more preferably methylene.
• oxy group ethyleneoxy group, propyleneoxy group, oxytrimethylene group, butyleneoxy group, oxytetramethylene group, pentyleneoxy group, heptyleneoxy group, octyleneoxy group, dimethyleneoxy group, diethyleneoxy group or dipropyleneoxy group is the base.
• divalent organic group for L 1 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• the trivalent organic group of L 1 is a group in which any one hydrogen atom in the above divalent organic group is replaced with a bond, preferably an alkylene group having 1 to 50 carbon atoms or a A group in which any one hydrogen atom of 1 to 50 alkyleneoxy groups is replaced with a bond.
• Specific examples of the alkylene group having 1 to 50 carbon atoms and the alkyleneoxy group having 1 to 50 carbon atoms are the same as above.
• Examples of the divalent organic group for L 2 include the same divalent organic groups as those for L 1 .
• the silicone chain-containing functional group of R 2 is preferably a group represented by the following general formula (1-C).
• R 11 is an alkyl group having 1 to 6 carbon atoms or a group represented by —OSi(R 16 ) 3 (each R 16 is independently an alkyl group having 1 to 3 carbon atoms);
• R 12 is an alkyl group having 1 to 6 carbon atoms or a group represented by —OSi(R 17 ) 3 (each R 17 is independently an alkyl group having 1 to 3 carbon atoms);
• R 13 is an alkyl group having 1 to 6 carbon atoms,
• R 14 is an alkyl group having 1 to 6 carbon atoms,
• R 15 is an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 or more.
• R 11 , R 12 , R 13 , R 14 , R 16 and R 17 are preferably methyl groups and R 15 is preferably an alkyl group having 1 to 6 carbon atoms.
• the divalent silicone chain-containing functional group of R3 is preferably a group represented by the general formula (SILICONE).
• the polymerizable monomer (1) is preferably a compound represented by the following general formula (1-1).
• R 11 is an alkyl group having 1 to 6 carbon atoms or a group represented by —OSi(R 17 ) 3 (each R 17 is independently an alkyl group having 1 to 3 carbon atoms);
• R 12 is an alkyl group having 1 to 6 carbon atoms or a group represented by —OSi(R 18 ) 3 (each R 18 is independently an alkyl group having 1 to 3 carbon atoms);
• R 13 is an alkyl group having 1 to 6 carbon atoms,
• R 14 is an alkyl group having 1 to 6 carbon atoms,
• R 15 is an alkyl group having 1 to 6 carbon atoms,
• R 16 is a hydrogen atom or a methyl group,
• L 1 is a divalent organic group, n is an integer of 0 or more.
• the polymerizable monomer (1) may be used singly or in combination of two or more.
• the polymerizable monomer (1) can be produced by a known method. Moreover, a commercial item may be used for the polymerizable monomer (1).
• the (poly)oxyalkylene chain-containing group of the polymerizable monomer (2) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.
• the group containing the (poly)oxyalkylene chain possessed by the polymerizable monomer (2) is used as the lubricating base oil of the lubricating oil composition.
• it can exhibit compatibility with lubricating oil additives other than antifoaming agents.
• Examples of the polymerizable monomer (2) having a group containing a polyoxyalkylene chain and having a (meth)acryloyl group as the polymerizable unsaturated group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth) Acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol/propylene glycol) mono(meth)acrylate, polyethylene glycol/polypropylene glycol mono(meth)acrylate, poly(ethylene) glycol/tetramethylene glycol) mono(meth)acrylate, polyethylene glycol/polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol/tetramethylene glycol) mono(meth)acrylate, polypropylene glycol/polytetramethylene glycol mono(meth)acrylate ) acrylate, poly(propylene glycol/tet
• poly(ethylene glycol/propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
• polyethylene glycol/polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol.
• Polymerizable monomer (2) is preferably a compound represented by the following general formula (2-1).
• R 21 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a phenyl group
• R 22 is a hydrogen atom or a methyl group
• n is an integer ranging from 1 to 4
• m is an integer ranging from 1 to 4
• p and q are each independently an integer ranging from 0 to 200 and satisfy p+q ⁇ 1.
• the alkyl group having 1 to 30 carbon atoms for R 21 may be any of a linear alkyl group, a branched alkyl group and a cyclic alkyl group, and specific examples are methyl group, ethyl group, normal propyl group, isopropyl group, n -butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group, adamantyl group, norbornyl group, dicyclopentanyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group, stearyl group, and the like.
• the alkyl group having 1 to 30 carbon atoms for R 21 is preferably an alkyl group having 1 to 25 carbon atoms, more preferably a cyclic alkyl group having 3 to 14 carbon atoms.
• the portion of the repeating unit bracketed by p and the repeating unit bracketed by q is the repeating unit bracketed by p and the repeating unit bracketed by q. It may be a random copolymer structure or a block copolymer structure of repeating units bracketed by p and repeating units bracketed by q.
• the polymerizable monomer (2) may be used singly or in combination of two or more.
• the polymerizable monomer (2) can be produced by a known method. Moreover, a commercial item may be used for the polymerizable monomer (2).
• the polymer of the present invention is a copolymer having a polymerizable monomer (1) and a polymerizable monomer (2) as polymerization components, and the polymerization form of the copolymer is not particularly limited.
• a random copolymer of the monomer (1) and the polymerizable monomer (2) may be used, or a block copolymer of the polymerizable monomer (1) and the polymerizable monomer (2) may be used.
• the content ratio of the structure derived from the polymerizable monomer (1) is relative to the total amount of the polymer For example, it is 5% by mass or more, preferably 15% by mass or more, 35% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, and 60% by mass or more in this order.
• the upper limit of the content of the polymerizable monomer (1) is not particularly limited. preferred in order.
• the content of the polymerizable monomer (1) is a value based on the mass of the polymer of the present invention (weight of the polymerizable monomer (1)/weight of the polymer), and the polymer of the present invention It can be adjusted by the raw material charging ratio of the polymerizable monomer (1) when producing.
• the polymer of the present invention may be a polymer having the polymerizable monomer (1) and the polymerizable monomer (2) as polymerization components, and further has an alkyl group having 1 to 30 carbon atoms. It is preferable to contain the monomer (3).
• the alkyl group possessed by the polymerizable monomer (3) is an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 25 carbon atoms, more preferably an alkyl group having 3 to 14 carbon atoms. is an alkyl group.
• the above alkyl group may be linear or branched, or may be cyclic.
• Examples of the polymerizable monomer (3) having an alkyl group having 1 to 30 carbon atoms and having a (meth)acryloyl group as the polymerizable unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) Acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (me
• Examples of the polymerizable monomer (3) having an alkyl group having 1 to 30 carbon atoms and having a vinyl ether group as the polymerizable unsaturated group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n Alkyl vinyl ethers such as -butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; be done.
• Examples of the polymerizable monomer (3) having an alkyl group having 1 to 30 carbon atoms and having a (meth)acryloylamino group as the polymerizable unsaturated group include N,N-dimethylacrylamide, N,N- diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acryloylmorpholine and the like.
• Examples of the polymerizable monomer (3) having an alkyl group having 1 to 30 carbon atoms and having a maleimide group as the polymerizable unsaturated group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, cyclohexylmaleimide and the like.
• Polymerizable monomer (3) is preferably a compound represented by the following general formula (3-1).
• R 31 is an alkyl group having 1 to 30 carbon atoms
• R 32 is a hydrogen atom or a methyl group
• the alkyl group may be further substituted with an aromatic group, such as benzyl (meth) acrylate, 2-phenoxymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and the like. is mentioned.
• the polymer of the present invention may be any polymer containing polymerizable monomer (1), polymerizable monomer (2) and optionally polymerizable monomer (3) as polymerization components.
• Polymerizable monomers other than the polymerizable monomer (1), the polymerizable monomer (2) and the polymerizable monomer (3) may be included as polymerization components within a range that does not impair the effect.
• Examples of the other polymerizable monomers include a polymerizable monomer (4) having a fluorine-containing functional group and a polymerizable monomer (5) having an aromatic group.
• Examples of the fluorine-containing functional group possessed by the polymerizable monomer (4) include a fluorinated alkyl group having 1 to 6 carbon atoms and a group containing a poly(perfluoroalkylene ether) chain.
• the poly(perfluoroalkylene ether) chain is a structure represented by the following general formula (PFPE) in which divalent fluorocarbon groups and oxygen atoms are alternately linked.
• PFPE general formula
• each X is independently a perfluoroalkylene group, n4 is the number of repetitions. )
• the repeating unit portion enclosed by n4 is a random combination of the repeating units enclosed by n4. It may be a polymer structure or a block copolymer structure of repeating units bounded by n4.
• perfluoroalkylene group for X the following perfluoroalkylene groups (X-1) to (X-6) can be exemplified.
• the perfluoroalkylene group for X is preferably a perfluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoromethylene group or a perfluoroethylene group. More preferably, both a perfluoromethylene group and a perfluoroethylene group are present as X in the general formula (PFPE).
• PFPE general formula
• n4 is, for example, an integer in the range of 1 to 300, preferably an integer in the range of 2 to 200, more preferably an integer in the range of 3 to 100, still more preferably in the range of 6 to 70 and most preferably an integer in the range 12-50.
• the polymerizable monomer (4) is preferably one or more selected from the group consisting of compounds represented by the following general formula (4-1) and compounds represented by the following general formula (4-2). be.
• R 41 is a hydrogen atom or a methyl group
• L 41 is a divalent or trivalent organic group or a single bond
• L 42 is a divalent organic group or a single bond
• R 42 is a fluorine-containing functional group
• R 43 is a divalent fluorine-containing functional group
• x is an integer of 1 or 2;
• the divalent or trivalent organic group for L 41 includes the same divalent or trivalent organic group for L 1 described above.
• the divalent organic group for L 42 includes the same divalent organic group for L 2 as described above.
• R 43 is a group represented by the general formula (PFPE)
• specific examples of the compound represented by the general formula (4-2) include the following.
• n is each independently an integer ranging from 1 to 10.
• the aromatic group possessed by the polymerizable monomer (5) is preferably an aromatic group having 6 to 20 carbon atoms, more preferably a phenyl group, naphthyl group, anthracen-1-yl group or phenanthrene-1- is an yl group.
• Examples of the polymerizable monomer (5) having an aromatic group include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene and the like.
• the polymer of the present invention is preferably a polymer in which the polymer components are substantially composed of polymerizable monomer (1), polymerizable monomer (2) and optional polymerizable monomer (3), More preferably, the polymerizable component is a polymer consisting only of polymerizable monomer (1), polymerizable monomer (2) and optional polymerizable monomer (3).
• substantially means that the total content of the polymerizable monomer (1), the polymerizable monomer (2) and the optional polymerizable monomer (3) in the polymerization component is 80 % by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.
• the number average molecular weight (Mn) of the polymer of the present invention is preferably in the range of 1,000 to 50,000, more preferably in the range of 1,000 to 30,000, still more preferably in the range of 1,500 to It is in the range of 10,000.
• the weight average molecular weight (Mw) of the polymer of the present invention is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,500 to 150,000, still more preferably in the range of 2,000 to It is in the range of 100,000, particularly preferably in the range of 3,000 to 50,000.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene-equivalent values based on gel permeation chromatography (GPC) measurement.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer of the present invention are measured by the methods described in Examples.
• the method for producing the polymer of the present invention is not particularly limited, and the polymer can be produced by a known method.
• the polymer of the present invention can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, or the like.
• the radical polymerization method the polymer of the present invention can be produced by charging a polymerizable monomer mixture in an organic solvent and adding a general-purpose radical polymerization initiator.
• Various polymerization initiators can be used, for example, peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, diacyl peroxide, azobisisobutyronitrile , azo compounds such as dimethyl azobisisobutyrate and phenylazotriphenylmethane, and metal chelate compounds such as Mn(acac) 3 .
• peroxides such as t-butylperoxy-2-ethylhexanoate
• benzoyl peroxide diacyl peroxide
• azobisisobutyronitrile azo compounds
• azo compounds such as dimethyl azobisisobutyrate and phenylazotriphenylmethane
• metal chelate compounds such as Mn(acac) 3 .
• a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as ⁇ -mercaptopropyltrimethoxysilane may be used as a chain transfer agent. may be used as an additive for
• organic solvent examples include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone, methyl acetate and ethyl acetate.
• alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone, methyl acetate and ethyl acetate.
• the polymer of the present invention can also be produced by living polymerization such as living radical polymerization and living anion polymerization.
• living radical polymerization a dormant species whose active polymerization terminal is protected by an atom or atomic group reversibly generates a radical and reacts with a monomer to proceed with the propagating reaction, and the propagating reaction proceeds even if the first monomer is consumed. The ends can be reacted with sequentially added second monomers to obtain block polymers without loss of activity.
• living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), radical polymerization using organotellurium (TERP), and the like. is mentioned.
• ATRP is polymerized using an organic halide, a sulfonyl halide compound, or the like as a polymerization initiator and a metal complex composed of a transition metal compound and a ligand as a catalyst.
• polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, ⁇ , ⁇ '-dichloroxylene, ⁇ , ⁇ ' -dibromoxylene, hexakis( ⁇ -bromomethyl)benzene, 2-halogenated carboxylic acids having 1 to 6 carbon atoms (e.g. 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) and alkyl esters having 1 to 6 carbon atoms.
• alkyl esters having 1 to 6 carbon atoms of 2-halogenated carboxylic acids having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, 2- Examples include methyl bromopropionate and ethyl 2-bromoisobutyrate.
• Transition metal compounds that can be used in ATRP are those represented by Mn + Xn .
• the transition metal M n+ of the transition metal compound represented by M n+ X n includes Cu + , Cu 2+ , Fe 2+ , Fe 3+ , Ru 2+ , Ru 3+ , Cr 2+ , Cr 3+ , Mo 0 , Mo + , Mo 2+ , Mo 3+ , W 2+ , W 3+ , Rh 3+ , Rh 4+ , Co + , Co 2+ , Re 2+ , Re 3+ , Ni 0 , Ni + , Mn 3+ , Mn 4+ , V 2+ , V 3+ , Zn + , It can be selected from the group consisting of Zn2 + , Au + , Au2 + , Ag + and Ag2 + .
• X in the transition metal compound represented by M n+ X n is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO 4 ) 1/2 , (PO 4 ) 1/3 , (HPO 4 ) 1/ 2 , ( H2PO4 ), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate) , SeR11 , CN and R12COO .
• R 11 represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms); It represents a linear or branched alkyl group (preferably methyl group) having 1 to 6 carbon atoms which may be substituted 5 times (preferably 1 to 3 times with fluorine or chlorine).
• n represents the formal charge on the metal and is an integer of 0-7.
• the ligand compound capable of coordinating to the transition metal of the above transition metal compound includes one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms capable of coordinating with the transition metal via a ⁇ bond.
• the transition metal complex is not particularly limited, but is preferably a group 7, 8, 9, 10, or 11 transition metal complex, and more preferably zerovalent copper, monovalent copper, or divalent ruthenium. , divalent iron or divalent nickel complexes.
• Divalent ruthenium complexes include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichloro p-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, carbonylchlorohydridotris(triphenylphosphine)ruthenium and the like.
• bivalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.
• a solvent is preferably used in the living radical polymerization.
• solvents used in living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; and halogen solvents such as dichloromethane and dichloroethane.
• Solvents aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol and isopropanol; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide; mentioned.
• aromatic solvents such as toluene and xylene
• ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
• alcohol solvents such as methanol, ethanol and isopropanol
• aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide
• the polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.
• metals derived from the transition metal compound used in the polymerization may remain in the resulting polymer. Metals remaining in the resulting polymer may be removed using activated alumina or the like after the completion of the polymerization.
• the antifoaming agent of the present invention can be suitably used as an antifoaming agent for lubricating oil compositions, and the lubricating oil composition of the present invention contains the antifoaming agent of the present invention.
• the antifoaming agent of the present invention has high antifoaming performance and can be used without limitation in lubricating oil compositions for drive system equipment such as shock absorbers, transmissions and power steering of automobiles.
• the content of the antifoaming agent of the present invention in the lubricating oil composition of the present invention is not particularly limited, and is, for example, in the range of 1 to 1000 ppm by mass, preferably in the range of 5 to 700 ppm by mass based on the total amount of the lubricating oil composition. and more preferably in the range of 10 to 400 mass ppm.
• a known lubricating base oil can be used for the lubricating oil composition of the present invention, and may be a mineral oil, a synthetic oil, or a mixed oil of a mineral oil and a synthetic oil.
• the lubricating oil fraction obtained by vacuum distillation of the atmospheric residue obtained by atmospheric distillation of crude oil is subjected to solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic deasphalting.
• Mineral oils refined by one or more of waxing, hydrorefining, and the like include paraffinic mineral oils, naphthenic mineral oils, and the like. Also included are mineral oils produced by isomerizing mineral oil-based waxes and waxes produced by the Fischer-Tropsch process (GTL wax).
• Synthetic oils include polybutene, polyolefins such as ⁇ -olefin homopolymers and copolymers (e.g., ethylene- ⁇ -olefin copolymers), various esters such as polyol esters, dibasic acid esters, and phosphate esters, and polybutenes.
• Various ethers such as phenyl ether, polyglycols, alkylbenzenes, alkylnaphthalenes and the like are included.
• the lubricating base oil may be used singly or in combination of two or more.
• the kinematic viscosity at 100° C. of the lubricating base oil is preferably in the range of 2 to 20 mm 2 /s, more preferably in the range of 2 to 15 mm 2 /s, still more preferably in the range of 3 to 10 mm 2 /s. is.
• the kinematic viscosity at 100° C. of the lubricating base oil is within the above range, the evaporation loss is small and the power loss due to viscous resistance is not so large, so the effect of improving fuel efficiency can be easily obtained.
• the lubricating base oil preferably has a paraffin content (may be described as %Cp) by ndM ring analysis of 70% or more, more preferably 75% or more, and even more preferably 80% That's it.
• a paraffin content may be described as %Cp
• ndM ring analysis 70% or more, more preferably 75% or more, and even more preferably 80% That's it.
• the content of the lubricating base oil in the lubricating oil composition is, for example, in the range of 65 to 95% by mass of the total amount of the lubricating oil composition, preferably in the range of 70 to 95% by mass, more preferably 70 to 90% by mass % range.
• the lubricating oil composition of the present invention may contain the antifoaming agent and lubricating base oil of the present invention, and may further contain other additives.
• Other additives include ashless detergents, ashless friction modifiers, antiwear agents, extreme pressure agents, viscosity index improvers, metal deactivators, pour point depressants, and rust inhibitors. may contain. These additives may be used alone or in combination of two or more.
• Each content of other additives can be appropriately adjusted within a range that does not impair the effects of the present invention, based on the total amount of the lubricating oil composition, usually 0.001 to 25 mass%, preferably 0.005 to 20 % by mass, more preferably 0.01 to 15% by mass.
• the total content of other additives is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less, based on the total amount of the lubricating oil composition.
• Ashless detergents include alkenylsuccinimides such as alkenylsuccinic acid monoimides and alkenylsuccinic acid bisimides, and boron-modified alkenylsuccinimides.
• Ashless friction modifiers include, for example, aliphatic amines, fatty acid esters, fatty acid amides, fatty acids, fatty alcohols, aliphatic ether and the like.
• Anti-wear agents or extreme pressure agents include, for example, sulfur-containing compounds such as zinc dithiophosphate; sulfur- and phosphorus-containing antiwear agents such as thiophosphites, thiophosphates, thiophosphonates, and amine or metal salts thereof;
• Viscosity index improvers include, for example, polymethacrylates, dispersed polymethacrylates, olefin copolymers (e.g., ethylene-propylene copolymers), dispersed olefin copolymers, styrene copolymers (e.g., styrene-diene copolymer, styrene-isoprene copolymer, etc.).
• olefin copolymers e.g., ethylene-propylene copolymers
• styrene copolymers e.g., styrene-diene copolymer, styrene-isoprene copolymer, etc.
• metal deactivators examples include benzotriazole-based compounds, tolyltriazole-based compounds, imidazole-based compounds, and pyrimidine-based compounds.
• pour point depressants examples include ethylene-vinyl acetate copolymers, condensates of chlorinated paraffin and naphthalene, condensates of chlorinated paraffin and phenol, polymethacrylates, and polyalkylstyrenes.
• rust preventives examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene-equivalent values based on gel permeation chromatography (GPC) measurement.
• GPC gel permeation chromatography
• n (The repeating portion of n is about 65.)
• the weight average molecular weight (Mw) was 17,000.
• Synthesis Example 2 Synthesis of antifoaming agent (2)
• Polyoxyalkylene chain-containing functional groups and silicone chain-containing functional groups were formed in the same manner as in Synthesis Example 1, except that the amount of t-butylperoxy-2-ethylhexanoate, which is a radical polymerization initiator, was changed to 2 parts by mass.
• Defoamer (2) was prepared which is a polymer having a group.
• the weight average molecular weight (Mw) was 30,400.
• Synthesis Example 3 Synthesis of antifoaming agent (3)
• Synthesis Example 2 was repeated except that 50 parts by mass of the compound represented by the formula (A), 40 parts by mass of methoxypolyethylene glycol methacrylate (the number of repeating ethylene oxide chains is about 9), and 10 parts by mass of methyl acrylate were used.
• an antifoaming agent (3) which is a polymer having a polyoxyalkylene chain-containing functional group and a silicone chain-containing functional group, was obtained.
• the weight average molecular weight (Mw) was 29,900.
• Synthesis Example 4 Synthesis of antifoaming agent (4)
• Synthesis Example 1 except that 57 parts by mass of the compound represented by the formula (A), 37 parts by mass of methoxypolyethylene glycol methacrylate (the number of repeating ethylene oxide chains is about 9), and 6 parts by mass of dicyclopentanyl acrylate were used.
• an antifoaming agent (4) which is a polymer having a polyoxyalkylene chain-containing functional group, a silicone chain-containing functional group and a cyclic alkyl group, was obtained.
• the weight average molecular weight (Mw) was 43,200.
• a commercially available dimethyl silicone (“KF-96-60,000cs” manufactured by Shin-Etsu Silicone Co., Ltd.) represented below was separately prepared as an antifoaming agent (1').
• lubricating oil composition Based on lubricating base oil (paraffinic mineral oil), various additives (viscosity index improver, phosphite ester compound, thiadiazole compound, calcium-based detergent, metal deactivator, ashless dispersant, antioxidant etc.) was added to 100 parts by mass of the base lubricating oil containing a small amount of the antifoaming agent shown in Table 1 with the dilution solvent shown in Table 1 in the amount shown in Table 1 to prepare a lubricating oil composition.
• base oil paraffinic mineral oil
• various additives viscosity index improver, phosphite ester compound, thiadiazole compound, calcium-based detergent, metal deactivator, ashless dispersant, antioxidant etc.

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• 2022
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