Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • 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
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index

Definitions

• the present invention relates to a lubricating oil composition, a lubricating oil viscosity modifier, and a polymer compound.
• Patent Document 1 discloses a method for obtaining a lubricating oil composition having predetermined viscosity characteristics by blending a predetermined viscosity index improver containing a comb polymer with a base oil.
• an object of the present invention is to provide a lubricating oil composition whose viscosity can be reversibly changed.
• the present invention also provides a lubricating oil viscosity modifier capable of reversibly changing the viscosity of a lubricating oil composition, and a polymer compound that can be suitably used as the lubricating oil viscosity modifier. With the goal.
• One aspect of the invention includes a base oil, a first compound having a first reactive site, and a second compound having a second reactive site, wherein the first reactive site and the second reactive site wherein one of the reactive sites of is a diene site and the other is a dienophile site.
• the first compound has a first reaction site
• the second compound has a second reaction site
• the first reaction site and the second reaction site are cyclized It consists of combinations that can be combined by an addition reaction (Diels-Alder reaction).
• Diels-Alder reaction Combining the first compound and the second compound through a cycloaddition reaction between the first reactive site and the second reactive site produces a compound with a large molecular weight in the lubricating oil composition, The viscosity of the oil composition increases.
• the cycloaddition reaction is a reversible reaction
• the first compound and the second compound are dissociated by the reverse reaction of the cycloaddition reaction (reverse Diels-Alder reaction), and the lubricating oil composition is converted to the initial state. state can be restored. Therefore, the lubricating oil composition can arbitrarily and reversibly switch between a low-viscosity state and a high-viscosity state by a cycloaddition reaction and its reverse reaction.
• the first compound may be a polymer compound containing a structural unit (A) having the first reactive site and a structural unit (C) having an alkyl group having 5 or more carbon atoms.
• a polymer compound can greatly change the molecular weight in the lubricating oil composition and has excellent compatibility with the base oil, so that the above effects can be obtained more remarkably.
• the molar ratio (C/A) of the structural unit (C) to the structural unit (A) may be 1 or more.
• the second compound may be a compound having two or more second reactive sites.
• the second compound functions as a cross-linking agent, so that the molecular weight of the compound can be efficiently increased or decreased in the lubricating oil composition, and the above-described effects can be exhibited more remarkably.
• the second compound may be a polymer compound containing a structural unit (B) having the second reactive site. Since such a polymer compound can greatly change the molecular weight in the lubricating oil composition, it is possible to obtain the above effects more significantly.
• the second compound may further contain a structural unit (C) having an alkyl group with 5 or more carbon atoms. Since such a second compound is excellent in compatibility with the base oil, the above-mentioned effects are exhibited more remarkably.
• the molar ratio (C/B) of the structural unit (C) to the structural unit (B) may be 1 or more.
• the first compound and the second compound are polymers containing a structural unit (A) having the first reactive site and a structural unit (B) having the second reactive site It may be a compound. Since such a polymer compound can greatly change the molecular weight in the lubricating oil composition, it is possible to obtain the above effects more significantly.
• the first compound and the second compound may further contain a structural unit (C) having an alkyl group with 5 or more carbon atoms. Since such a first compound and a second compound are excellent in compatibility with the base oil, the above-mentioned effects are exhibited more remarkably.
• the molar ratio (C/(A+B)) of the structural unit (C) to the total of the structural unit (A) and the structural unit (B) is 1 or more. It may be a molecular compound.
• the diene moiety may be selected from the group consisting of a group having a butadiene skeleton and a group having an anthracene ring.
• the dienophile portion may be a portion containing at least one group selected from the group consisting of vinyl groups, vinylene groups and vinylidene groups.
• Another aspect of the present invention is a lubricating oil composition obtained by subjecting at least one of the first reactive sites and at least one of the second reactive sites in the lubricating oil composition to a cycloaddition reaction. Regarding.
• Yet another aspect of the present invention includes a first compound having a first reactive site and a second compound having a second reactive site, wherein the first reactive site and the second reactive site are It relates to a lubricating oil viscosity modifier, wherein one of the reaction sites is a diene site and the other is a dienophile site.
• Still another aspect of the present invention is a first structural unit having at least one reactive site selected from the group consisting of a diene site and a dienophile site, and a second structural unit having an alkyl group having 5 or more carbon atoms. And, it relates to a polymer compound containing.
• the molar ratio of the second structural unit to the first structural unit may be 1 or more.
• a lubricating oil composition whose viscosity can be reversibly changed is provided. Further, according to the present invention, a lubricating oil viscosity modifier capable of reversibly changing the viscosity of a lubricating oil composition, and a polymer compound suitably used as the lubricating oil viscosity modifier are provided. be done.
• the lubricating oil composition of this embodiment comprises a base oil, a first compound having a first reactive site, and a second compound having a second reactive site.
• one of the first reactive site and the second reactive site is a diene site and the other is a dienophile site.
• the first compound has a first reactive site
• the second compound has a second reactive site
• the first reactive site and the second reactive site are cycloaddition reactions. It is composed of combinations that can be combined by (Diels-Alder reaction). Therefore, by combining the first compound and the second compound through a cycloaddition reaction between the first reaction site and the second reaction site, a compound having a large molecular weight is produced in the lubricating oil composition. and increase the viscosity of the lubricating oil composition.
• the cycloaddition reaction is a reversible reaction
• the first compound and the second compound are separated by the reverse reaction (reverse Diels-Alder reaction) of the cycloaddition reaction, thereby initializing the lubricating oil composition. state can be restored.
• the molecular weight of the compound in the lubricating oil composition can be increased or decreased by the cycloaddition reaction of the first compound and the second compound and the reverse reaction thereof, whereby the lubricating oil composition Viscosity can be increased or decreased.
• the lubricating oil composition of the present embodiment can arbitrarily and reversibly switch between a low-viscosity state and a high-viscosity state through a cycloaddition reaction and its reverse reaction.
• a diene site is a site having two conjugated carbon-carbon double bonds (conjugated diene), and can also be called a conjugated diene site.
• the diene site is not particularly limited as long as it is a site capable of undergoing a cycloaddition reaction with the dienophile site.
• the diene moiety includes, for example, a group having a butadiene skeleton, a group having an anthracene ring, and the like.
• groups having a butadiene skeleton include butadienyl groups (1-butadienyl group, 2-butadienyl group), groups having a cyclopentadienyl ring (eg, cyclopentadienyl group), and 1,3-cyclohexadienyl rings.
• a furan ring-containing group e.g., furyl group (2-furyl group, 3-furyl group)
• a thiophene ring-containing group e.g., thiophenyl group ( 2-thiophenyl group, 3-thiophenyl group)
• a group having a pyrrole ring eg, pyrrolyl group (1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group)
• a group having a cyclopentadienyl ring, a group having a furan ring, and a group having a pyrrole ring are preferred from the viewpoint of stability in the lubricating oil composition and better reactivity in the cycloaddition reaction.
• a group having a furan ring is more preferred.
• Groups having a butadiene skeleton include, for example, groups represented by the following formulas (a-1-1) to (a-1-12).
• formulas (a-1-3), (a-1-4), (a-1 -7), (a-1-8), (a-1-10) or (a-1-11) is preferably a group represented by formula (a-1-3), (a-1-4 ), (a-1-7) or (a-1-8) are more preferred.
• the group having a butadiene skeleton may be a group in which some or all of the hydrogen atoms in the above group are substituted with substituents.
• Substituents may be, for example, halogeno groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, formyl groups, acyl groups, alkoxycarbonyl groups, etc., preferably alkyl groups, alkoxy groups, aryl groups and aryloxy groups. It is a group selected from the group consisting of groups, more preferably a group selected from the group consisting of alkyl groups and alkoxy groups. These substituents may further have a substituent.
• Groups having an anthracene ring include, for example, 1-anthracenyl group, 2-anthracenyl group, 1-naphthacene group, 2-naphthacene group, 3-benzo[a]anthracenyl group, 4-benzo[a]anthracenyl group, 5- benzo[a]anthracenyl group, 6-benzo[a]anthracenyl group, 7-benzo[a]anthracenyl group, 8-benzo[a]anthracenyl group and the like.
• 1-anthracenyl group and 2-anthracenyl group are preferred.
• Groups having an anthracene ring include, for example, groups represented by the following formulas (a-2-1) to (a-2-10).
• a group having an anthracene ring may be a group in which some or all of the hydrogen atoms of the above group are substituted with a substituent.
• Substituents may be, for example, halogeno groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, formyl groups, acyl groups, alkoxycarbonyl groups, etc., preferably alkyl groups, alkoxy groups, aryl groups and aryloxy groups. It is a group selected from the group consisting of groups, more preferably a group selected from the group consisting of alkyl groups and alkoxy groups. These substituents may further have a substituent.
• an anthracene ring-containing group is preferable, and a furan ring-containing group and an anthracene ring-containing group are more preferable.
• the diene site preferably has a high diene electron density from the viewpoint of excellent reactivity in the cycloaddition reaction.
• the diene sites may have electron donating groups to increase the electron density of the conjugated diene.
• the electron-donating group for example, an alkyl group, an alkoxy group, or the like is preferable.
• the dienophile site is not particularly limited as long as it has a carbon-carbon double bond and is capable of undergoing a cycloaddition reaction with the diene site.
• the dienophile moiety includes, for example, a vinyl group (group represented by the following formula (b-1-1)), a vinylene group (represented by the following formula (b-1-2) or (b-1-3) group) and a vinylidene group (group represented by the following formula (1-b-4)).
• dienophile moieties include unsaturated hydrocarbon groups (e.g., vinyl groups and alkenyl groups), (meth)acryloyl groups, groups obtained by removing one hydrogen atom from (meth)acrylonitrile, and groups having a maleimide ring (e.g., , maleimide group), maleate ester group (eg, maleic acid monoester group, maleic acid diester group), maleic acid thioester group (eg, maleic acid monothioester group, maleic acid dithioester group), and the like.
• unsaturated hydrocarbon groups e.g., vinyl groups and alkenyl groups
• (meth)acryloyl groups groups obtained by removing one hydrogen atom from (meth)acrylonitrile
• groups having a maleimide ring e.g., maleimide group
• maleate ester group eg, maleic acid monoester group, maleic acid diester group
• maleic acid thioester group eg
• the dienophile moiety includes, for example, groups represented by the following formulas (b-2-1) to (b-2-14).
• formulas (b-2-2), (b-2-3), (b-2 -6), (b-2-7), (b-2-8), (b-2-9) or (b-2-10) is preferably a group represented by formula (b-2-2 ), (b-2-3), (b-2-6) or (b-2-9) are more preferred.
• R 1 , R 2 and R 3 each independently represent a monovalent group.
• R 1 may be, for example, an alkyl group or an aryl group, and these groups may have a substituent.
• R 2 and R 3 may be, for example, an alkyl group or an aryl group, and these groups may have substituents.
• the dienophile moiety may be a group in which some or all of the hydrogen atoms of the above group are substituted with a substituent.
• the substituent may be, for example, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, a formyl group, an acyl group, an alkoxycarbonyl group, a nitrile group, etc., preferably an alkyl group, an aryl group, a formyl group, It is a group selected from the group consisting of an acyl group and a nitrile group. These substituents may further have a substituent.
• the dienophile site preferably has a low electron density of the dienophile from the viewpoint of excellent reactivity in the cycloaddition reaction.
• the dienophile moieties may have electron withdrawing groups to reduce the electron density of the dienophile.
• electron-withdrawing groups include formyl groups, acyl groups, alkoxycarbonyl groups, nitrile groups and the like.
• the dienophile moiety may also be a group obtained by removing one or more hydrogen atoms from a cyclic conjugated enone containing a carbon-carbon double bond and a carbonyl group adjacent thereto.
• cyclic conjugated enones include compounds having a structure in which at least one carbon atom adjacent to an olefin in a 4- to 8-membered cycloalkene skeleton is substituted with a carbonyl group.
• cyclic conjugated enones include cyclopentenone, cyclopentenedione, cyclohexenone, cyclohexenedione, cycloheptenone, cycloheptenedione, cyclooctenone, cyclooctenedione, and the like. Cyclic conjugated enones also include compounds represented by the following formulas (b-3-1) to (b-3-8).
• the cyclic conjugated enone may have a condensed ring of a cycloalkene ring and another ring (eg, cycloalkane ring, aromatic ring, etc.) for stabilization of the cycloalkene skeleton.
• a condensed ring of a cycloalkene ring and another ring eg, cycloalkane ring, aromatic ring, etc.
• Cyclic conjugated enones having condensed rings include indenone, naphthalene-1(4H)-one, naphthalene-1,4-dione, 8,9-dihydro-5H-benzo[7]annulene-5- one, 5H-benzo[7]annulene-5,8-(9H)-dione, (Z)-9,10-dihydrobenzo[8]annulene-5(8H)-one, (Z)-9,10- and dihydrobenzo[8]annulene-5,8dione.
• Cyclic conjugated enones having a condensed ring also include compounds represented by the following formulas (b-4-1) to (b-4-7).
• substituents include alkyl groups, aryl groups, aralkyl groups, alkyloxy groups, aryloxy groups, formyl groups, acyl groups, ester groups, amide groups, amino groups, hydroxy groups, alkoxycarbonyl groups, nitrile groups, and the like. preferably a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, a formyl group, an acyl group, an ester group, an amide group, an amine group, a hydroxy group and a nitrile group. These substituents may further have a substituent.
• the cyclic conjugated enone may be one in which two or more of the above cyclic conjugated enones are linked by a linking group.
• Examples of such cyclic conjugated enones include compounds linked via an alkylene chain, polyalkyleneoxy chain, or the like (eg, compounds represented by the following formula (b-5-1)).
• X represents a group represented by -R- or -OR- (R is a group exemplified as a spacer described later).
• a monomer obtained by substituting a portion of the hydrogen atoms of the cyclic conjugated enone described above with a substituent containing a (meth)acryloyl group may be used as the first compound or the second compound.
• R' represents a hydrogen atom or a methyl group.
• One of the first reaction site and the second reaction site is a diene site, and the other is a dienophile site. That is, when the first reactive site is a diene site, the second reactive site is a dienophile site, and when the first reactive site is a dienophile site, the second reactive site is a diene site.
• the first reactive site is preferably bound to the main chain via a spacer.
• the second reactive site is preferably bound to the polymer chain via a spacer. This tends to further improve the reactivity of the cycloaddition reaction.
• spacers include alkanediyl groups, alkyleneoxy groups, and polyalkyleneoxy groups.
• the alkanediyl group may be, for example, an alkanediyl group having 1 to 1000 carbon atoms.
• the number of carbon atoms in the alkanediyl group is preferably 1-500, more preferably 1-100, and may be 1-50, 1-20 or 1-10.
• alkanediyl groups include methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, and octanediyl groups. These groups may have a substituent.
• the alkyleneoxy group may be, for example, an alkyleneoxy group having 1 to 1000 carbon atoms.
• the number of carbon atoms in the alkyleneoxy group is preferably 1-500, more preferably 1-100, and may be 1-50, 1-20 or 1-10.
• alkyleneoxy group examples include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butadieneoxy group, a 1,2-butyleneoxy group, a 1,3-butyleneoxy group and a 1,4-butyleneoxy group. be done. These groups may have a substituent.
• polyalkyleneoxy groups include groups in which a plurality of the above-described alkyleneoxy groups are linked.
• polyalkyleneoxy groups examples include polyethyleneoxy groups, polypropyleneoxy groups, and polybutadieneoxy groups. These groups may have a substituent.
• a polyethyleneoxy group and a polypropyleneoxy group are preferable from the viewpoint of easy availability.
• These groups may be formed by utilizing the terminal hydroxyl groups of polyalkylene oxides (eg, polyethylene oxide, polypropylene oxide, etc.) to introduce first and/or second reactive sites.
• the spacer may be, for example, a group represented by formula (S-1) or (S-2) below.
• R11 represents a hydrogen atom or an alkyl group
• R12 represents a hydrogen atom or an alkyl group
• R13 represents an alkanediyl group
• n1 represents an integer of 1 or more
• n2 represents an integer of 1 or more. Indicates an integer.
• n 1 is 2 or more
• a plurality of R 11 and R 12 may be the same or different.
• n 2 is 2 or more, multiple R 13 may be the same or different.
• n1 is, for example, 1000 or less, preferably 500 or less, more preferably 100 or less, and may be 50 or less, 20 or less, or 10 or less.
• the alkyl group for R 11 and R 12 may be, for example, an alkyl group having 1 to 12 carbon atoms.
• n2 is, for example, 10000 or less, preferably 5000 or less, more preferably 1000 or less, and may be 50 or less, 20 or less, or 10 or less.
• the alkanediyl group for R 13 may be, for example, an alkanediyl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms).
• the total content of the first compound and the second compound in the lubricating oil composition may be, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, relative to 100 parts by mass of the base oil. , more preferably 0.1 parts by mass or more. Further, the total content of the first compound and the second compound in the lubricating oil composition may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, with respect to 100 parts by mass of the base oil. Preferably, it is 30 parts by mass or less.
• the first compound is a polymer compound having a first reaction site
• the second compound is a polymer compound having two second reaction sites.
• a first embodiment in which the compound has the above a second embodiment in which the first compound is a polymer compound having the first reaction site, and the second compound is a polymer compound having the second reaction site, and a third embodiment in which both the first compound and the second compound are polymer compounds having a first reaction site and a second reaction site.
• the first compound is a polymer compound (hereinafter referred to as polymer compound (1)) containing a structural unit (A) having a first reactive site.
• the polymer compound (1) preferably further contains a structural unit (C) having an alkyl group with 5 or more carbon atoms. Since such a polymer compound (1) is excellent in compatibility with the base oil, it is possible to obtain the above effects more significantly.
• the number of carbon atoms in the alkyl group of the structural unit (C) is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more, from the viewpoint of further improving compatibility with the base oil. Further, the number of carbon atoms in the alkyl group of the structural unit (C) is not particularly limited to the upper limit, and may be, for example, 1000 or less, 500 or less, 100 or less, 50 or less, 40 or less, or 30 or less. Or it may be 20 or less.
• the molar ratio (C/A) of the structural unit (C) to the structural unit (A) may be, for example, 1 or more, from the viewpoint of further improving the compatibility with the base oil. , preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2 or more. Further, in the polymer compound (1), the molar ratio (C/A) of the structural unit (C) to the structural unit (A) may be, for example, 1000 or less, so that the effect of increasing the molecular weight by the cycloaddition reaction can be further enhanced. From the viewpoint of obtaining a remarkable degree, it is preferably 800 or less, more preferably 500 or less, and still more preferably 300 or less.
• the polymer compound (1) may further contain a structural unit (X) other than the structural unit (A) and the structural unit (C).
• the ratio of the structural unit (A) to the total structural units may be, for example, 0.01 mol% or more, from the viewpoint of obtaining a more pronounced effect of increasing the molecular weight by the cycloaddition reaction. is preferably 0.05 mol % or more, more preferably 0.1 mol % or more, and still more preferably 0.2 mol % or more.
• the ratio of the structural unit (C) to all structural units may be, for example, 10 mol% or more, and from the viewpoint of further improving the compatibility with the base oil, it is preferably 20 mol. % or more, more preferably 30 mol % or more, and still more preferably 40 mol % or more. Further, in the polymer compound (1), the ratio of the structural unit (C) to the total structural units may be, for example, 99.99 mol% or less, preferably 99.95 mol% or less, more preferably 99.99 mol% or less. It is 9 mol % or less, more preferably 99.8 mol % or less, still more preferably 99.6 mol % or less.
• the ratio of the structural unit (X) to the total structural units is not particularly limited, and is, for example, 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and 60 It may be mol % or less, 50 mol % or less, 40 mol % or less, 30 mol % or less, 20 mol % or less, 10 mol % or less, 5 mol % or less, or 1 mol % or less.
• the ratio of the structural unit (X) to all structural units may be, for example, 0.0001 mol% or more, and may be 0.001 mol% or more. It may be present, and may be 0.01 mol % or more.
• all structural units means a value calculated as one structural unit from a partial structure derived from one monomer, and structural unit (A), structural unit (C) and structural unit (X). It can also be said that the total amount of In the present specification, the “structural unit” can also be referred to as a monomer unit or a partial structure derived from the monomer unit.
• the polymer compound (1) may be, for example, a polymer of a monomer component containing the monomer (a), or a monomer component containing the monomer (a) and the monomer (c). or a polymer of monomer components containing the monomer (a), the monomer (c) and the monomer (x).
• the monomer (a) is a monomer that forms the structural unit (A) by polymerization, or a monomer that forms the structural unit (A') that is converted to the structural unit (A) after polymerization.
• the monomer (c) is a monomer that forms the structural unit (C) by polymerization, or a monomer that forms the structural unit (C') that is converted to the structural unit (C) after polymerization.
• the monomer (x) is a monomer that forms the structural unit (X) by polymerization, or a monomer that forms the structural unit (X') that is converted to the structural unit (X) after polymerization.
• polymer compound (1) a polymer compound (1-1) having a carbon chain as the main chain is preferable.
• the monomer (a) is, for example, maleic anhydride, maleic acid derivative, maleimide, maleimide derivative, (meth)acrylic acid, (meth ) acrylic esters and the like. These monomers (a) form a polymer compound having a structural unit (A) or a structural unit (A').
• a polymer compound having a structural unit (A') is formed, a reactive group capable of reacting with the structural unit (A') (for example, when the monomer (a) is maleic anhydride, amino group, hydroxy group, etc.) and a first reaction site, and reacting the compound with the structural unit (A'), a polymer compound having the structural unit (A) can be produced.
• the monomer (c) may be, for example, an alkyl (meth)acrylate having an alkyl group with 5 or more carbon atoms. Such a monomer (c) forms a polymer compound having a structural unit (C).
• the monomer (x) may be, for example, an alkyl (meth)acrylate having an alkyl group with 4 or less carbon atoms.
• the structural unit (A) may be, for example, a structural unit represented by the following formula (A-1), (A-2) or (A-3).
• L A1 represents a spacer and R A1 represents a first reaction site.
• L A2 represents a spacer, R A2 represents a first reaction site, and R 21 represents a hydrogen atom or a methyl group.
• L A3 represents a spacer and R A3 represents a first reaction site.
• L A1 , L A2 and L A3 may be the spacers described above.
• L A1 , L A2 and L A3 may be, for example, an alkanediyl group, an alkyleneoxy group or a polyalkyleneoxy group, preferably a group represented by formula (S-1) or (S-2) .
• the first reactive site in R A1 and R A2 may be the diene or dienophile moiety described above.
• R A1 , R A2 and R A3 are groups represented by formulas (a-1-1) to (a-1-12), or groups represented by formulas (a-2-1) to (a- 2-10), preferably a group represented by formulas (a-1-3), (a-1-4), (a-1-7), (a-1-8), ( a-2-1) or a group represented by (a-2-2).
• R A1 , R A2 and R A3 may be groups represented by formulas (b-2-1) to (b-2-14), preferably groups represented by formula (b-2- 2), (b-2-3), (b-2-6), (b-2-7), (b-2-8) (b-2-9) or (b-2-10) and more preferably a group represented by formula (b-2-2), (b-2-3), (b-2-6) or (b-2-9).
• the structural unit (C) may be, for example, a structural unit represented by the following formula (C-1).
• R 1 C1 represents an alkyl group having 5 or more carbon atoms
• R 2 C2 represents a hydrogen atom or a methyl group.
• the number average molecular weight (Mn) of the polymer compound (1) is not particularly limited, and may be, for example, 300 or more. From the viewpoint of obtaining the above effects more significantly, it is preferably 700 or more, more preferably 800 or more. Yes, and may be 1000 or more. Further, the number average molecular weight (Mn) of the polymer compound (1) may be, for example, 1,000,000 or less, and from the viewpoint of better solubility in the base oil, it is preferably 500,000 or less, more preferably 400,000 or less. , 300000 or less.
• the molecular weight distribution (Mw/Mn) of the polymer compound (1) is not particularly limited, and may be, for example, 20 or less, preferably 10 or less from the viewpoint of easier control of the molecular weight before and after the cycloaddition reaction. , more preferably 5 or less, and may be 3 or less. Moreover, the molecular weight distribution (Mw/Mn) of the polymer compound (1) may be, for example, 1.0 or more, or may be 1.1 or more.
• the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of polymer compounds indicate values obtained in terms of polystyrene by the GPC method.
• the content of the polymer compound (1) in the lubricating oil composition may be, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 100 parts by mass of the base oil. It is 0.1 parts by mass or more. Further, the content of the polymer compound (1) in the lubricating oil composition may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the base oil. It is below the department.
• the second compound is a compound having two or more second reactive sites.
• Such a second compound functions as a cross-linking agent that cross-links the polymer compound (1).
• the number of second reaction sites possessed by the second compound may be, for example, 5 or less, and from the viewpoint of suppressing excessive cross-linking reaction, it is preferably 4 or less, more preferably 3 or less, and preferably 2. More preferred.
• the second compound may have a structure in which a plurality of second reactive sites are linked by a linking group.
• the linking group is preferably a hydrocarbon group, more preferably an arylene group, an alkanediyl group, or a combination thereof.
• the content of the second compound in the lubricating oil composition is not particularly limited. It is preferable that the ratio (M 2 /M 1 ) of the total number of moles (M 2 ) of is 0.1-10.
• the ratio (M 2 /M 1 ) is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. Also, the ratio (M 2 /M 1 ) is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
• the total content of the polymer compound (1) and the second compound in the lubricating oil composition may be, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass, relative to 100 parts by mass of the base oil. part or more, more preferably 0.1 part by mass or more. Further, the total content of the polymer compound (1) and the second compound in the lubricating oil composition may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, relative to 100 parts by mass of the base oil. , more preferably 30 parts by mass or less.
• the first compound is a polymer compound (polymer compound (1)) containing a structural unit (A) having a first reactive site.
• polymer compound (1) in the second aspect the same compounds as the polymer compound (1) in the first aspect can be exemplified.
• the second polymer compound is a polymer compound (polymer compound (2)) containing a structural unit (B) having a second reactive site.
• polymer compound (2) a polymer compound in which the structural unit (A) in the polymer compound (1) is replaced with the structural unit (B) can be exemplified.
• the polymer compound (2) preferably further contains a structural unit (C) having an alkyl group with 5 or more carbon atoms. Since such a polymer compound (2) has excellent compatibility with the base oil, it is possible to obtain the above effects more significantly.
• the structural unit (C) the same structural unit (C) as in the polymer compound (1) can be exemplified.
• the molar ratio (C/B) of the structural unit (C) to the structural unit (B) may be, for example, 1 or more, from the viewpoint of further improving the compatibility with the base oil. , preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2 or more. Further, in the polymer compound (2), the molar ratio (C/B) of the structural unit (C) to the structural unit (B) may be, for example, 1000 or less, so that the effect of increasing the molecular weight by the cycloaddition reaction can be further enhanced. From the viewpoint of obtaining a remarkable degree, it is preferably 800 or less, more preferably 500 or less, and still more preferably 300 or less.
• the polymer compound (2) may further contain a structural unit (Y) other than the structural unit (B) and the structural unit (C).
• the ratio of the structural unit (B) to the total structural units may be, for example, 0.01 mol% or more, from the viewpoint of obtaining a more pronounced effect of increasing the molecular weight by the cycloaddition reaction. is preferably 0.05 mol % or more, more preferably 0.1 mol % or more, and still more preferably 0.2 mol % or more.
• the ratio of the structural unit (B) to the total structural units may be, for example, 50 mol% or less, and compatibility with the base oil of the high molecular weight after the cycloaddition reaction is preferably 40 mol % or less, more preferably 30 mol % or less, still more preferably 20 mol % or less, from the viewpoint of further improving the
• the ratio of the structural unit (C) to all structural units may be, for example, 10 mol% or more, and from the viewpoint of further improving the compatibility with the base oil, it is preferably 20 mol. % or more, more preferably 30 mol % or more, and still more preferably 40 mol % or more. Further, in the polymer compound (2), the ratio of the structural unit (C) to all structural units may be, for example, 99.99 mol% or less, preferably 99.95 mol% or less, more preferably 99.99 mol% or less. It is 9 mol % or less, more preferably 99.8 mol % or less, still more preferably 99.6 mol % or less.
• the ratio of the structural unit (Y) to the total structural units is not particularly limited, and is, for example, 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less. It may be mol % or less, 50 mol % or less, 40 mol % or less, 30 mol % or less, 20 mol % or less, 10 mol % or less, 5 mol % or less, or 1 mol % or less.
• the ratio of the structural unit (Y) to all structural units may be, for example, 0.0001 mol% or more, and may be 0.001 mol% or more. It may be present, and may be 0.01 mol % or more.
• all structural units means a value calculated with a partial structure derived from one monomer as one structural unit, and the structural unit (B), the structural unit (C) and the structural unit (Y). It can also be said that the total amount of
• the polymer compound (2) may be, for example, a polymer of a monomer component containing the monomer (b), or a monomer component containing the monomer (b) and the monomer (c). or a polymer of monomer components containing the monomer (b), the monomer (c) and the monomer (y).
• the monomer (b) is a monomer that forms the structural unit (B) by polymerization, or a monomer that forms the structural unit (B') that is converted to the structural unit (B) after polymerization.
• the monomer (c) is a monomer that forms the structural unit (C) by polymerization, or a monomer that forms the structural unit (C') that is converted to the structural unit (C) after polymerization.
• the monomer (y) is a monomer that forms the structural unit (Y) by polymerization, or a monomer that forms the structural unit (Y') that is converted to the structural unit (Y) after polymerization.
• polymer compound (2) a polymer compound (2-1) having a carbon chain as the main chain is preferable.
• the monomer (b) is, for example, maleic anhydride, maleic acid derivative, maleimide, maleimide derivative, (meth)acrylic acid, (meth ) acrylic esters and the like. These monomers (b) form a polymer compound having a structural unit (B) or a structural unit (B').
• a reactive group capable of reacting with the structural unit (B') for example, when the monomer (b) is maleic anhydride, amino group, hydroxy group, etc.
• a second reactive site for example, when the monomer (b) is maleic anhydride, amino group, hydroxy group, etc.
• the monomer (c) may be, for example, an alkyl (meth)acrylate having an alkyl group with 5 or more carbon atoms. Such a monomer (c) forms a polymer compound having a structural unit (C).
• the monomer (y) may be, for example, an alkyl (meth)acrylate having an alkyl group with 4 or less carbon atoms.
• the structural unit (B) may be, for example, a structural unit represented by the following formula (B-1), (B-2) or (B-3).
• L B1 represents a spacer and R B1 represents a second reactive site.
• L B2 represents a spacer
• R B2 represents a second reaction site
• R 31 represents a hydrogen atom or a methyl group.
• L B3 represents a spacer
• R B3 represents a second reaction site.
• L B1 , L B2 and L B3 may be the spacers described above.
• L B1 , L B2 and L B3 may be, for example, an alkanediyl group, an alkyleneoxy group or a polyalkyleneoxy group, preferably a group represented by formula (S-1) or (S-2) .
• the second reactive sites in R B1 , R B2 and R B2 may be the diene or dienophile sites described above.
• R B1 , R B2 and R B3 may be groups represented by formulas (b-2-1) to (b-2-14), preferably (b-2-2), (b-2-3), (b-2-6), (b-2-7), (b-2-8), (b-2-9) or (b-2-10) is preferred, more preferably formula (b-2-2), (b-2-3), (b-2-6) or (b-2-9).
• R B1 , R B2 and R B3 are groups represented by formulas (a-1-1) to (a-1-12), or groups represented by formulas (a-2-1) to ( a-2-10), preferably a group represented by formulas (a-1-3), (a-1-4), (a-1-7), (a-1-8) , (a-2-1) or (a-2-2).
• the structural unit (C) may be, for example, a structural unit represented by the above formula (C-1).
• the number average molecular weight (Mn) of the polymer compound (2) is not particularly limited, and may be, for example, 300 or more. From the viewpoint of obtaining the above effects more significantly, it is preferably 700 or more, more preferably 800 or more. Yes, and may be 1000 or more.
• the number average molecular weight (Mn) of the polymer compound (2) may be, for example, 1,000,000 or less, preferably 500,000 or less, more preferably 400,000 or less from the viewpoint of better solubility in the base oil. , 300000 or less.
• the molecular weight distribution (Mw/Mn) of the polymer compound (2) is not particularly limited, and may be, for example, 20 or less, preferably 10 or less from the viewpoint of easier control of the molecular weight before and after the cycloaddition reaction. , more preferably 5 or less, and may be 3 or less. Moreover, the molecular weight distribution (Mw/Mn) of the polymer compound (2) may be, for example, 1.0 or more, or may be 1.1 or more.
• the total content of the polymer compound (1) and the polymer compound (2) in the lubricating oil composition is, for example, 0.001 parts by mass or more with respect to 100 parts by mass of the base oil. Well, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more.
• the content of the polymer compound (1) and the polymer compound (2) in the lubricating oil composition may be, for example, 50 parts by mass or less, preferably 40 parts by mass, relative to 100 parts by mass of the base oil. Below, more preferably 30 mass parts or less.
• the content ratio of the polymer compound (1) and the polymer compound (2) in the lubricating oil composition is not particularly limited, but from the viewpoint of obtaining the above effects more remarkably, the first It is preferable that the ratio (M 2 /M 1 ) of the total number of moles ( M 2 ) of the second reaction sites to the total number of moles (M 1 ) of the reaction sites is 0.1-10.
• the ratio (M 2 /M 1 ) is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. Also, the ratio (M 2 /M 1 ) is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
• the first compound and the second compound are polymer compounds (hereinafter referred to as , polymer compound (3)).
• the first compound and the second compound may be the same polymer compound. That is, the lubricating oil composition according to the third aspect is a base oil, a polymer compound containing a structural unit (A) having a first reactive site and a structural unit (B) having a second reactive site ( 3) and may be a lubricating oil composition containing.
• the molar ratio (B/A) of the structural unit (B) to the structural unit (A) is, for example, 0.2 or more, preferably 0.3 or more, and more preferably 0.5. That's it.
• the molar ratio (B/A) is, for example, 5 or less, preferably 3 or less, more preferably 2 or less.
• the polymer compound (3) preferably further contains a structural unit (C) having an alkyl group with 5 or more carbon atoms. Since such a polymer compound (3) has excellent compatibility with the base oil, it is possible to more significantly obtain the above effects.
• a structural unit (C) the same structural unit (C) as in the polymer compound (1) can be exemplified.
• the molar ratio (C/(A+B)) of the structural unit (C) to the total of the structural unit (A) and the structural unit (B) may be, for example, 1 or more. is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2 or more, from the viewpoint of further improving the compatibility of .
• the molar ratio (C/(A+B)) may be, for example, 1000 or less, preferably 800 or less, more preferably 500 or less, and even more preferably 300 or less.
• the polymer compound (3) may further contain a structural unit (Z) other than the structural unit (A), the structural unit (B) and the structural unit (C).
• the total ratio of the structural units (A) and the structural units (B) to the total structural units may be, for example, 0.01 mol% or more, and the effect of increasing the molecular weight by the cycloaddition reaction is preferably 0.05 mol % or more, more preferably 0.1 mol % or more, and still more preferably 0.2 mol % or more, from the viewpoint of obtaining the more remarkably.
• the total ratio of the structural units (A) and the structural units (B) to the total structural units may be, for example, 50 mol% or less, and the polymer after the cycloaddition reaction From the viewpoint of further improving the compatibility with the base oil, the content is preferably 40 mol% or less, more preferably 30 mol% or less, and still more preferably 20 mol% or less.
• the ratio of the structural unit (C) to all structural units may be, for example, 10 mol% or more, and from the viewpoint of further improving the compatibility with the base oil, it is preferably 20 mol. % or more, more preferably 30 mol % or more, and still more preferably 40 mol % or more. Further, in the polymer compound (3), the ratio of the structural unit (C) to all structural units may be, for example, 99.99 mol% or less, preferably 99.95 mol% or less, more preferably 99.99 mol% or less. It is 9 mol % or less, more preferably 99.8 mol % or less, still more preferably 99.6 mol % or less.
• the ratio of the structural unit (Z) to the total structural units is not particularly limited, and is, for example, 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and 60 It may be mol % or less, 50 mol % or less, 40 mol % or less, 30 mol % or less, 20 mol % or less, 10 mol % or less, 5 mol % or less, or 1 mol % or less.
• the ratio of the structural unit (Z) to all structural units may be, for example, 0.0001 mol% or more, and may be 0.001 mol% or more. It may be present, and may be 0.01 mol % or more.
• all structural units means a value calculated with a partial structure derived from one monomer as one structural unit, and structural unit (A), structural unit (B), and structural unit (C). and the total amount of the structural units (Z).
• the polymer compound (3) may be, for example, a polymer of monomer components containing the monomer (a) and the monomer (b), and the monomer (a), the monomer (b ) and a monomer component containing the monomer (c), the monomer (a), the monomer (b), the monomer (c) and the monomer (z) It may be a polymer of monomer components containing.
• the monomer (a) is a monomer that forms the structural unit (A) by polymerization, or a monomer that forms the structural unit (A') that is converted to the structural unit (A) after polymerization.
• the monomer (b) is a monomer that forms the structural unit (B) by polymerization, or a monomer that forms the structural unit (B') that is converted to the structural unit (A) after polymerization.
• the monomer (c) is a monomer that forms the structural unit (C) by polymerization, or a monomer that forms the structural unit (C') that is converted to the structural unit (C) after polymerization.
• the monomer (z) is a monomer that forms the structural unit (Z) by polymerization, or a monomer that forms the structural unit (Z') that is converted to the structural unit (z) after polymerization.
• polymer compound (3) a polymer compound (3-1) having a carbon chain as the main chain is preferable.
• the monomer (a) is, for example, maleic anhydride, a maleic acid derivative, maleimide, a maleimide derivative, (meth)acrylic acid, (meth ) acrylic esters and the like. These monomers (a) form a polymer compound having a structural unit (A) or a structural unit (A').
• a reactive group capable of reacting with the structural unit (A') for example, when the monomer (a) is maleic anhydride, amino group, hydroxy group, etc.
• a first reaction site for example, when the monomer (a) is maleic anhydride, amino group, hydroxy group, etc.
• a polymer compound having the structural unit (A) can be produced.
• the monomer (b) is, for example, maleic anhydride, maleic acid derivative, maleimide, maleimide derivative, (meth)acrylic acid, (meth ) acrylic esters and the like. These monomers (b) form a polymer compound having a structural unit (B) or a structural unit (B').
• a polymer compound having a structural unit (B') is formed, a reactive group capable of reacting with the structural unit (B') (for example, when the monomer (b) is maleic anhydride, amino group, hydroxy group, etc.) and a second reactive site, and reacting the compound with the structural unit (B') to form a polymer compound having the structural unit (B).
• the monomer (a) and the monomer (b) may be the same or different.
• the monomer (c) may be, for example, an alkyl (meth)acrylate having an alkyl group with 5 or more carbon atoms. These monomers (c) form a polymer compound having structural units (C).
• the monomer (z) may be, for example, an alkyl (meth)acrylate having an alkyl group with 4 or less carbon atoms.
• the structural unit (A) may be, for example, a structural unit represented by the above formula (A-1) or (A-2), and the structural unit (B) is For example, it may be a structural unit represented by the above formula (B-1) or (B-2), and the structural unit (C) is, for example, a structural unit represented by the above formula (C-1). you can
• the number average molecular weight (Mn) of the polymer compound (3) is not particularly limited, and may be, for example, 300 or more, and from the viewpoint of obtaining the above effects more remarkably, it is preferably 700 or more, more preferably 800 or more. Yes, and may be 1000 or more.
• the number average molecular weight (Mn) of the polymer compound (3) may be, for example, 1,000,000 or less, and from the viewpoint of better solubility in the base oil, it is preferably 500,000 or less, more preferably 400,000 or less. , 300000 or less.
• the molecular weight distribution (Mw/Mn) of the polymer compound (3) is not particularly limited, and may be, for example, 20 or less, preferably 10 or less from the viewpoint of easier control of the molecular weight before and after the cycloaddition reaction. , more preferably 5 or less, and may be 3 or less. Moreover, the molecular weight distribution (Mw/Mn) of the polymer compound (3) may be, for example, 1.0 or more, or may be 1.1 or more.
• the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of polymer compounds indicate values obtained in terms of polystyrene by the GPC method.
• the content of the polymer compound (3) in the lubricating oil composition may be, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass, relative to 100 parts by mass of the base oil. part or more, more preferably 0.1 part by mass or more. Further, the content of the polymer compound (3) in the lubricating oil composition may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the base oil. It is below the department.
• the base oil (lubricant base oil) is not particularly limited, and for example, it can be appropriately selected from known base oils and used.
• base oils include mineral oils and synthetic oils.
• Mineral oils include, for example, atmospheric residual oil obtained by atmospheric distillation of crude oil, distillate oil obtained by vacuum distillation of the atmospheric residual oil, and solvents such as solvent deasphalting and solvent extraction in the distillate oil. Treatment, hydrocracking, solvent dewaxing, dewaxing such as catalytic dewaxing, and refining such as hydrorefining. Further, it is also possible to use branched isomerized straight-chain waxes produced by the low polymerization Fischer-Tropsch method of ethylene or the like.
• Synthetic oils include, for example, polybutene, poly ⁇ -olefin, esterified oils of polyols, esterified oils based on dicarboxylic acid, phosphoric acid, etc., and polyalkylene glycols such as polyethylene glycol and polypropylene glycol.
• the kinematic viscosity of the base oil at 40° C. is not particularly limited, but is, for example, 1 mm 2 /s or more, preferably 5 mm 2 /s or more, more preferably 10 mm 2 /s or more. Also, the kinematic viscosity of the base oil at 40° C. is, for example, 100 mm 2 /s or less, preferably 90 mm 2 /s or less, more preferably 80 mm 2 /s or less.
• the kinematic viscosity of the base oil at 100° C. is not particularly limited, but is, for example, 0.1 mm 2 /s or more, preferably 0.5 mm 2 /s or more, more preferably 1 mm 2 /s or more. Also, the kinematic viscosity of the base oil at 100° C. is, for example, 40 mm 2 /s or less, preferably 30 mm 2 /s or less, more preferably 20 mm 2 /s or less.
• the viscosity index of the base oil may be, for example, 80 or higher, preferably 90 or higher, more preferably 100 or higher.
• the base oil may be selected in consideration of the 40°C kinematic viscosity, 100°C kinematic viscosity, viscosity index, etc., according to the properties of the desired lubricating oil composition.
• kinematic viscosity at 40°C As used herein, kinematic viscosity at 40°C, kinematic viscosity at 100°C, and viscosity index are measured with a rheometer, and the measured viscosity is calculated based on the density of the base oil at 40°C or 100°C. Shows the value obtained by converting to
• the content of the base oil in the lubricating oil composition may be, for example, 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and 65 % by mass or more, 70% by mass or more, or 75% by mass or more.
• the lubricating oil composition may further contain other components (hereinafter also referred to as additives) other than the base oil, the first compound and the second compound.
• additives include, for example, metallic detergents, dispersants, antiwear agents, extreme pressure agents, antioxidants, pour point depressants, antifoaming agents, friction modifiers, rust inhibitors, metal deactivators, and the like. is mentioned.
• the content of additives in the lubricating oil composition is not particularly limited.
• the content of the additive in the lubricating oil composition, based on the total amount of the lubricating oil composition, may be, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and 0 % by mass.
• the base oil, the first compound and the second compound may be selected according to the desired properties of the lubricating oil composition.
• the kinematic viscosity of the lubricating oil composition at 40°C is preferably higher than that of the base oil at 40°C. If the first compound and/or the second compound are polymeric compounds, the kinematic viscosity at 40°C of the lubricating oil composition tends to be higher than the kinematic viscosity at 40°C of the base oil.
• the kinematic viscosity at 40°C of the lubricating oil composition is not particularly limited.
• the kinematic viscosity of the lubricating oil composition at 40° C. may be, for example, 1 mm 2 /s or more, preferably 5 mm 2 /s or more, more preferably 10 mm 2 /s or more.
• the kinematic viscosity of the lubricating oil composition at 40° C. is, for example, 150 mm 2 /s or less, preferably 130 mm 2 /s or less, more preferably 100 mm 2 /s or less.
• the kinematic viscosity at 100°C of the lubricating oil composition is preferably higher than the kinematic viscosity at 100°C of the base oil. If the first compound and/or the second compound are polymer compounds, the kinematic viscosity at 100°C of the lubricating oil composition tends to be higher than the kinematic viscosity at 100°C of the base oil.
• the kinematic viscosity at 100° C. of the lubricating oil composition is not particularly limited, but is, for example, 0.1 mm 2 /s or more, preferably 0.5 mm 2 /s or more, more preferably 1 mm 2 /s or more.
• the kinematic viscosity at 100° C. of the lubricating oil composition is, for example, 50 mm 2 /s or less, preferably 40 mm 2 /s or less, more preferably 30 mm 2 /s or less.
• the viscosity index of the lubricating oil composition is preferably higher than that of the base oil. If the first compound and/or the second compound are polymeric compounds, the viscosity index of the lubricating oil composition tends to be higher than that of the base oil.
• the viscosity index of the lubricating oil composition may be, for example, 80 or higher, preferably 90 or higher, more preferably 100 or higher.
• the first reaction site of the first compound and the second reaction site of the second compound in the lubricating oil composition are subjected to a cycloaddition reaction to form a high molecular weight body, and more A highly viscous lubricating oil composition can be obtained.
• the lubricating oil composition before the cycloaddition reaction is referred to as the lubricating oil composition (i)
• the lubricating oil composition after the cycloaddition reaction is referred to as the lubricating oil composition (ii).
• the kinematic viscosity of the lubricating oil composition (ii) at 40°C is higher than the kinematic viscosity of the lubricating oil composition (i) at 40°C.
• the kinematic viscosity of the lubricating oil composition (ii) at 40° C. is not particularly limited, but is, for example, 1 mm 2 /s or more, preferably 5 mm 2 /s or more, more preferably 10 mm 2 /s or more.
• the kinematic viscosity of the lubricating oil composition (ii) at 40° C. is, for example, 200 mm 2 /s or less, preferably 150 mm 2 /s or less, more preferably 130 mm 2 /s or less.
• the kinematic viscosity of the lubricating oil composition (ii) at 100°C is higher than the kinematic viscosity of the lubricating oil composition (i) at 100°C.
• the kinematic viscosity of the lubricating oil composition (ii) at 100° C. is not particularly limited, but is, for example, 0.1 mm 2 /s or more, preferably 0.5 mm 2 /s or more, more preferably 1 mm 2 /s or more.
• the kinematic viscosity at 100° C. of the lubricating oil composition (ii) is, for example, 70 mm 2 /s or less, preferably 60 mm 2 /s or less, more preferably 50 mm 2 /s or less.
• the viscosity index of the lubricating oil composition (ii) may be, for example, 80 or higher, preferably 90 or higher, more preferably 100 or higher.
• the conditions for carrying out the cycloaddition reaction are not particularly limited, but examples include a method of heating the lubricating oil composition (i) to a predetermined reaction temperature.
• the cycloaddition reaction may be carried out by heating the lubricating oil composition (i) under the environment of use.
• the reaction temperature for the cycloaddition reaction is not particularly limited, and may be appropriately selected according to the amount and type of the first reaction site and the second reaction site.
• the reaction temperature for the cycloaddition reaction may be, for example, 70° C. or higher, or 100° C. or higher.
• the reaction temperature of the cycloaddition reaction may be, for example, 200° C. or lower, or may be 190° C. or lower.
• the reaction time of the cycloaddition reaction is not particularly limited, and may be appropriately selected according to the amount and type of the first reaction site and the second reaction site.
• the reaction time of the cycloaddition reaction may be, for example, 1 second or longer, 1 minute or longer, 30 minutes or longer, or 1 hour or longer.
• the reaction time of the cycloaddition reaction may be, for example, 48 hours or less, or may be 24 hours or less.
• the lubricating oil composition (ii) returns the high molecular weight substance to the first compound and the second compound by the reverse reaction of the cycloaddition reaction (hereinafter also simply referred to as the reverse reaction), thereby lubricating It can be converted into oil composition (i).
• the conditions for carrying out the reverse reaction are not particularly limited, but examples include a method of heating the lubricating oil composition (ii) to a predetermined reaction temperature.
• the reaction temperature for the reverse reaction is not particularly limited, and may be appropriately selected according to the amount and type of the first reaction site and the second reaction site.
• the reaction temperature of the reverse reaction may be, for example, 100° C. or higher, or 110° C. or higher.
• the reaction temperature of the reverse reaction may be, for example, 300° C. or lower, or may be 280° C. or lower.
• the reaction time of the reverse reaction is not particularly limited, and may be appropriately selected according to the amount and type of the first reaction site and the second reaction site.
• the reaction time of the reverse reaction may be, for example, 1 second or longer, 1 minute or longer, 30 minutes or longer, or 1 hour or longer.
• the reaction time of the reverse reaction may be, for example, 48 hours or less, or may be 24 hours or less.
• the lubricating oil composition of the present embodiment is optionally reversibly reversible to a low viscosity state (lubricating oil composition (i)) by a cycloaddition reaction of the first compound and the second compound and the reverse reaction thereof. high viscosity state (lubricating oil composition (ii)).
• the use of the lubricating oil composition of the present embodiment is not particularly limited, and for example, it may be used in a temperature range that matches the reaction conditions of the cycloaddition reaction and its reverse reaction.
• the lubricating oil composition of the present embodiment can be reused by, for example, using it in a temperature range that matches the cycloaddition reaction conditions and exposing it to reverse reaction conditions after use.
• the lubricating oil composition of the present embodiment can be suitably used for applications such as engine oil, gear oil, turbine oil, and sliding surface oil for automobiles, ships, and the like.
• the lubricating oil viscosity modifier of one embodiment comprises a first compound having a first reactive site and a second compound having a second reactive site.
• first compound and the second compound the same compounds as the first compound and the second compound in the above lubricating oil composition can be exemplified.
• the viscosity modifier comprises a high molecular weight compound having a first compound having a first reactive site and a second compound having a second reactive site linked by a cycloaddition reaction.
• a high molecular weight substance can be easily decomposed into the first compound and the second compound by the reverse reaction of the cycloaddition reaction, and therefore can be suitably used as the above viscosity modifier.
• One aspect of the present invention may be, for example, the following (1) to (16).
• the first compound and the second compound are polymer compounds containing a structural unit (A) having the first reactive site and a structural unit (B) having the second reactive site, The lubricating oil composition according to (1).
• the molar ratio (C/(A+B)) of the structural unit (C) to the total of the structural unit (A) and the structural unit (B) is 1 or more.
• a polymer compound comprising a first structural unit having at least one reactive site selected from the group consisting of a diene site and a dienophile site, and a second structural unit having an alkyl group having 5 or more carbon atoms.
• Mn and Mw of polymer compounds were measured by the following methods. Two columns (TSKgel superHM-N) were connected to a GPC device (Shimadzu RID-10A/CBM-20A/DGU-20A3, LC-20AD/DPD-20M A/CTO-20A) and a differential refractive index detector. and A sample obtained by adding 1 mL of a chloroform solvent to 1 mg of the sample was analyzed at 40° C. at a flow rate of 0.3 mL/min to measure the molecular weight (number average molecular weight Mn and weight average molecular weight Mw). Monodisperse polystyrene was used as the calibration sample.
• the viscosity was measured by the following method, Using a rheometer device (manufactured by TA Instruments-Waters LLC, Discovery HR-20 WS type), samples were sandwiched between Smart Swap Peltier plates (SUS 60 mm plate, with solvent trap) (gap 500 microns ), and the viscosity was measured from room temperature to 200°C at a heating rate of 5°C/min.
• Example 1-1 Production of polymer compound (A1)
• a 30 mL eggplant-shaped flask was charged with tetrahydrofuran (THF, 5 mL), where maleic anhydride (MA, 248 mg, 2.52 mmol), methyl methacrylate (MMA, 252 mg, 2.52 mmol), 2-ethylhexyl methacrylate (EHMA, 2 .0 g, 10.1 mmol), dodecyl methacrylate (DMA, 2.58 g, 10.1 mmol) was added. Further, azoisobutyronitrile (41.4 mg, 0.252 mmol) was added and reacted at 65° C.
• the polymer compound (a1) was obtained as a viscous solid through reprecipitation purification using methanol. Yield was 59%.
• the obtained polymer compound (a1) had Mn of 59000 and Mw/Mn of 1.8.
• the polymer compound (a1) was confirmed to be a quaternary copolymer by 1 H-NMR measured after dissolving in deuterated chloroform.
• the content of MA units in the polymer compound (a1) was 5 mol % with respect to the total amount of monomer units.
• polymer compound (a1) was dissolved in THF (6 ml), 10 equivalents of furfurylamine (241 mg, 2.49 mmol) was added to the MA unit in the polymer compound (a1), and the mixture was heated at 5°C for 5 hours. Further, acetic anhydride (1.0 mL) and pyridine (1.0 mL) were added and reacted at 40° C. for 12 hours to convert to an imide form. Polymer compound (A1) was obtained as a colorless viscous solid through reprecipitation purification in methanol. Yield was 77%. The obtained polymer compound (A1) had Mn of 57000 and Mw/Mn of 2.0. It was confirmed that the polymer compound (A1) obtained was soluble in GrIII base oil (Yubase 4) and poly- ⁇ -olefin (PAO, Durasyn 164).
• Example 1-2 Production of lubricating oil composition (1) and lubricating oil composition (1')
• Polymer compound (A1) (165 mg, Mn: 57000, Mw/Mn: 2.0) obtained in Example 1-1 was dissolved in 3 g of poly- ⁇ -olefin (PAO, Durasyn 164), and then 4,4′-Bismaleimidodiphenylmethane (2.79 mg, 0.0078 mmol) was added to obtain a lubricating oil composition (1).
• the obtained lubricating oil composition (1) was heated at 80° C. for 3 hours to obtain a lubricating oil composition (1′).
• the molecular weight distribution was compared with the molecular weight of the polymer compound (A1) in the lubricating oil composition (1). It was confirmed that the molecular weight shifted to the high molecular weight side. In addition, a peak of the low molecular weight component and a peak of the high molecular weight component were observed. was 6. From this result, it was confirmed that the molecular weight of the lubricating oil composition was increased by the cycloaddition reaction. The lubricating oil composition (1′) was then heated at 130° C. for 2 hours.
• Example 2-1 Production of polymer compound (A2)
• THF tetrahydrofuran
• FMA furfuryl methacrylate
• MMA methyl methacrylate
• EHMA 2-ethylhexyl methacrylate
• DMA dodecyl methacrylate
• Polymer compound (A2) was obtained as a colorless viscous solid with a yield of 67% through reprecipitation purification using methanol.
• the obtained polymer compound (A2) had Mn of 36000 and Mw/Mn of 2.0. It was confirmed that the polymer compound (A2) obtained was soluble in poly- ⁇ -olefin (PAO, Durasyn 164). Further, it was confirmed by NMR that the polymer compound (A2) obtained was a quaternary copolymer (FMA 5 mol %, MMA 5 mol %, EHMA 30%, DMA 60%).
• Example 2-2 Production of lubricating oil composition (2) and lubricating oil composition (2')
• PAO Polymer compound (A2) (370 mg, furyl group 0.082 mmol) was dissolved in 3.08 g of PAO (Durasyn 164), and the previously prepared bismaleimide solution was added to polymer compound (A2).
• a lubricating oil composition (2) was obtained by adding 0.5 equivalent to the furyl group.
• the lubricating oil composition (2) was heated at 80° C. for 12 hours to obtain a lubricating oil composition (2′).
• the integrated value of the peak derived from the furyl group and the integrated value of the peak derived from the maleimide group of 4,4′-bismaleimidediphenylmethane were 4, It decreased with respect to the integrated value of the peak of the hydrogen atom on the benzene ring of 4'-bismaleimidodiphenylmethane.
• Example 3-1 Production of polymer compound (A3')
• N-(2-Hydroxyethyl)maleimide (35.7mmol) and 9-hydroxymethylanthracene (35.7mmol) were dissolved in toluene (35mL) and reacted at 110°C for 24 hours to effect cycloaddition reaction. got a body
• This adduct (26.5 mmol) was dissolved in THF (170 mL), methacrylic acid chloride (103 mmol) and triethylamine (57.7 mmol) were added at 0° C., and the mixture was reacted at room temperature for 48 hours.
• dimethacrylate After extraction with chloroform, washing with an aqueous sodium hydrogencarbonate solution and saturated brine, and column purification using silica gel (solvent: chloroform), a dimethacrylate was obtained with a yield of 32%.
• the dimethacrylate obtained here (13.4 mg, 0.0276 mmol), 2-ethylhexyl methacrylate (EHMA, 0.242 ml, 1.08 mmol), dodecyl methacrylate (DMA, 0.484 ml, 1.65 mmol) were combined with THF ( 3 ml), azoisobutyronitrile (4.53 mg, 0.0276 mmol, 1 mol %) was added and reacted at 65° C. for 3 hours.
• Polymer compound (A3′) was obtained as a colorless viscous solid with a yield of 65% through reprecipitation purification in methanol.
• the obtained polymer compound (A3') had Mn of 77000 and Mw/Mn of 2.4, and was soluble in poly- ⁇ -olefin (PAO, Durasyn 164). Further, it was confirmed by NMR that the polymer compound (A3′) obtained was a terpolymer (1.0 mol % of dimethacrylate, 39 mol % of EHMA, and 60 mol % of DMA).
• the polymer compound (A3′) corresponds to a polymer crosslinked by a cycloaddition reaction between an anthracenyl group as a diene moiety and a maleimide group as a dienophile moiety.
• Example 3-2 Production of lubricating oil composition (3′) and lubricating oil composition (3)
• Polymer compound (A3′) (0.205 g, Mn: 77000) was dissolved in PAO (2.13 g) to obtain lubricating oil composition (3′).
• the obtained lubricating oil composition (3′) was reacted at 200° C. for 24 hours to obtain a lubricating oil composition (3).
• Mn 22000 and Mw/Mn was 1.3. From this result, it was confirmed that the reverse reaction of the cycloaddition reaction can cleave the crosslinked site of the polymer.
• the viscosity of the lubricating oil composition (3′) was measured with a rheometer under the temperature conditions of holding at 25° C. for 5 minutes, raising the temperature to 200° C. at a heating rate of 5° C./min, and holding for 20 minutes.
• the viscosity at 40° C. was 37.9 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 47.3 mm 2 /s.
• the viscosity at 100° C. was 11.3 mPa ⁇ s
• the kinematic viscosity converted from the specific gravity was 14.9 mm 2 /s.
• a viscosity index of 330 was calculated from these kinematic viscosities.
• the viscosity of the lubricating oil composition (3) is measured with a rheometer at 25 ° C. for 5 minutes, heated to 200 ° C. at a temperature increase rate of 5 ° C./min, and maintained for 20 minutes. It was measured.
• the viscosity at 40° C. was 25.1 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 31.4 mm 2 /s.
• the viscosity at 100° C. was 4.97 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 6.6 mm 2 /s.
• a viscosity index of 173 was calculated from these kinematic viscosities.
• Example 3-1 Kinematic viscosity of base oil
• the PAO used in Example 3-2 had a kinematic viscosity of 17.2 mm 2 /s at 40°C and a kinematic viscosity of 3.9 mm 2 /s at 100°C. Also, the PAO used in Example 3-2 was heated at 200° C. for 24 hours, but there was no significant difference in viscosity before and after heating.
• Example 4-1 Production of polymer compound (A4')
• N-Methoxycarbonylmaleimide (0.197 g, 1.27 mmol)
• Example 4-2 Production of lubricating oil composition (4) and lubricating oil composition (4')
• the polymer compound in the obtained lubricating oil composition (4) had an Mn of 78000 and an Mw/Mn of 1.3. Then, the lubricating oil composition (4) was reacted at 100° C. for 6 hours to obtain a lubricating oil composition (4′).
• the polymer compound in the obtained lubricating oil composition (4') had an Mn of 160,000 and an Mw/Mn of 2.8. From this result, it was confirmed that the molecular weight of the polymer compound in the lubricating oil composition can be changed by the cycloaddition reaction between the furyl group and the maleimide group and the reverse reaction thereof.
• Example 5-1 Production of polymer compound (A5)
• Triethylamine (5.0 mmol) and methacrylic acid chloride (6.3 mmol) were added to a dichloromethane solution of 11-furyl-1-undecanol (1.26 mmol) under an argon atmosphere at 0° C. and reacted at room temperature for 18 hours.
• Extraction with dichloromethane and washing with an aqueous solution of sodium bicarbonate gave a brown liquid furan-containing methacrylate with a yield of 86%.
• Example 5-2 Production of lubricating oil composition (5) and lubricating oil composition (5')
• Polymer compound (A5) was dissolved in PAO (Durasyn 164) to prepare a 10 wt% solution.
• PAO dimaleimide
• the PAO solution concentration: 10% by mass
• BMI-BATD bismaleimide
• cyclohexanone was added to obtain a lubricating oil composition (5).
• the obtained lubricating oil composition (5) was reacted at 100° C. for 1.5 hours to obtain a lubricating oil composition (5′).
• the peak derived from the furyl group decreased in 1 H-NMR, confirming the progress of the cycloaddition reaction.
• the lubricating oil composition (5') was then reacted at 135°C for 24 hours.
• a furyl group-derived peak appeared in 1 H-NMR, confirming the progress of the reverse reaction of the cycloaddition reaction.
• the viscosity of the lubricating oil composition (5) was measured with a rheometer by maintaining the temperature at 25°C for 5 minutes and increasing the temperature to 100°C at a rate of 5°C/min. The viscosity at 40° C.
• the viscosity of the obtained lubricating oil composition (5') was measured by a rheometer by keeping the composition at 25°C for 5 minutes and heating it up to 100°C at a heating rate of 5°C/min.
• the viscosity at 40° C. was 59.3 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 74.08 mm 2 /s.
• the viscosity at 100° C. was 15.3 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 20.17 mm 2 /s.
• a viscosity index of 296 was calculated from these kinematic viscosities.
• Example 6-1 Production of polymer compound (A6)
• Dichloromethane (50 ml) and triethylamine (2.0 ml) were added to dissolve 9-hydroxymethylanthracene (2.0 g, 9.6 mmol), and methacryloyl chloride (1.50 g, 14.4 mmol) was added thereto at 0°C. was slowly added and allowed to react for 8 hours.
• the reaction mixture was then diluted with 200 ml of chloroform and washed with a saturated aqueous sodium hydrogencarbonate solution.
• Anthracene-containing methacrylate (a6) (1.0 g, 3.6 mmol), 2-ethylhexyl methacrylate (5.0 g, 25.2 mmol), and dodecyl methacrylate (1.0 g, 43.3 mmol) were then added to tetrahydrofuran (20 ml).
• Example 6-2 Production of lubricating oil composition (6) and lubricating oil composition (6')
• Polymer compound (A6) (1.0 g) was dissolved in PAO (Durasyn 164) (5.0 g).
• PAO Densyn 164
• TMI cross-linking agent
• 15 mg an amount that gives 1 equivalent of the maleimide group to the anthracene ring of the polymer compound (A6))
• Example 7-1 Synthesis of polymer compound (A7)
• 5-hydroxy-1,4-naphthoquinone (1.0 g, 5.74 mmol) and 9-hydroxymethylanthracene (1.32 g, 6.31 mmol) were added to toluene (50 ml) and reacted at 110° C. for 48 hours, A cycloadduct (a7-1) was synthesized.
• Cycloadduct (a7) (0.292 g, 0.76 mmol), triethylamine (5 equivalents) were then dissolved in dichloromethane (7 ml) and methacryloyl chloride (0.476 g, 5.58 mmol) was added at 0°C. The reaction was allowed to proceed for 48 hours.
• the reaction solution was washed with a saturated aqueous sodium hydrogencarbonate solution and saturated brine, and purified by HPLC using chloroform-5% triethylamine as a developing solution to synthesize a yellow viscous solid dimethacrylate (a7-2).
• the resulting dimethacrylate (65 mg, 0.126 mmol), 2-ethylhexyl methacrylate (176 mg, 0.89 mmol), dodecyl methacrylate (387 mg, 1.52 mmol), THF (1.0 ml) and AIBN (4.15 mg) were then , 0.025 mmol) and reacted at 65° C. for 20 hours to obtain a polymer compound (A7).
• Polymer compound (A7) was gelled, suggesting the formation of a crosslinked polymer capable of decrosslinking.
• Example 8-1 Production of polymer compound (A8)
• Furan-containing methacrylate used in Example 5-1 (60.0 mg, 0.196 mmol), 2-ethylhexyl methacrylate (0.31 mL, 1.37 mmol), dodecyl methacrylate (0.69 mL, 2.35 mmol) as initiator
• Azoisobutyronitrile (3.2 mg, 0.020 mmol) was dissolved in THF, degassed, reacted at 65° C. for 3 hours, and purified by reprecipitation using methanol to obtain polymer compound (A8). Obtained in 84% yield.
• Example 8-2 Production of lubricating oil composition (8) and lubricating oil composition (8')
• a 30% by weight solution of bis(2-ethylhexanoic acid) neopentyl of the polymer compound (A8) was prepared, and BMI-BATD synthesized in Production Example 1 was added thereto in the moles of the furyl group and the maleimide group in the polymer compound.
• a lubricating oil composition (8) was obtained by adding so that the ratio was 4:1. Further, the lubricating oil composition (8) was heated at 100° C. for 3 hours to obtain a lubricating oil composition (8′).
• the Mn of the polymer compound in the lubricating oil composition (8') was 55000, and the Mw/Mn was 2.7.
• the viscosity of the lubricating oil composition (8) was measured by a rheometer by holding the temperature at 25°C for 5 minutes and increasing the temperature to 100°C at a rate of 5°C/min.
• the viscosity at 40° C. was 44.0 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 55.0 mm 2 /s.
• the viscosity at 100° C. was 15.9 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 21.0 mm 2 /s.
• a viscosity index of 395 was calculated from these kinematic viscosities.
• the viscosity of the obtained lubricating oil composition (5') was measured by a rheometer by keeping the composition at 25°C for 5 minutes and heating it up to 100°C at a heating rate of 5°C/min.
• the viscosity at 40° C. was 48.1 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 60.1 mm 2 /s.
• the viscosity at 100° C. was 17.0 mPa ⁇ s, and the kinematic viscosity converted from the specific gravity was 22.4 mm 2 /s.
• a viscosity index of 388 was calculated from these kinematic viscosities.
• the viscosity of the lubricating oil composition can be changed by changing the molecular weight of the polymer compound in the lubricating oil composition by the cycloaddition reaction between the furyl group and the maleimide group and its reverse reaction. confirmed to be possible.
• Example 9-1 Production of lubricating oil composition (9) and lubricating oil composition (9')
• anthracene-modified PPG 35 mg
• the above hexamethylenebisnaphthoquinone 9.4 mg
• bis(2-ethylhexanoic acid) neopentyl 1.0 g
• This lubricating oil composition (9) was reacted at 110° C. for 15 hours to form an addition polymer of anthracene-modified PPG and hexamethylenebisnaphthoquinone.
• the Mn of the addition polymer formed was 4300 and Mw/Mn was 1.0.

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