Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/02—Hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
  • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
  • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

• the present invention provides a conjugated diene-based graft polymer having a high viscosity index and a good friction-reducing effect, a lubricating oil additive comprising the conjugated diene-based graft polymer, and an oil composition containing a base oil and the lubricating oil additive. Regarding.
• Lubricating oils may contain additives, commonly referred to as viscosity index improvers, as lubricating oil additives, for example to improve their viscosity properties.
• Viscosity index improvers are added to reduce temperature-dependent changes in the viscosity of lubricating oils. The higher the viscosity index, the smaller the change in viscosity, resulting in improved fuel economy performance of lubricating oils.
• Viscosity index improvers include, for example, olefin copolymers, polymethacrylates, styrene/hydrogenated diene block polymers, and the like. Viscosity index improvers are subjected to high shear in the environment in which they are used, so long-term use causes a decrease in viscosity due to a decrease in molecular weight, and the necessary lubricating performance is reduced. Due to the recent increase in environmental awareness, a viscosity index improver having higher shear stability is required.
• Viscosity index improvers made from star polymers are known to have better shear stability than linear polymers due to their molecular structure.
• Patent Document 1 describes that a viscosity index improver composed of star-shaped hydrogenated polyisoprene obtained by coupling living polyisoprene synthesized by anionic polymerization with divinylbenzene has excellent shear stability.
• Patent Document 2 discloses a mixture of a polymer having two active terminals serving as main chain constituents and a polymer having one active terminal serving as side chain constituents.
• a graft polymer synthesized by a method of adding a silicon atom-containing coupling agent having 3 or more reactive sites to this mixture and reacting it is described.
• a heteroatom such as a silicon atom derived from the coupling agent is contained at the branch point connecting the main chain and the side chain.
• Friction inhibitors which are classified as extreme pressure agents, friction modifiers, and anti-wear agents, are added to the lubricating oil for the purpose of extending the life of machinery by improving fuel efficiency and suppressing seizure. may be included as an agent.
• the present invention has been made in view of the above circumstances, a new polymer having a high viscosity index and a good friction reducing effect, a lubricating oil additive comprising the polymer, and an improved viscosity index comprising the polymer agent, a friction inhibitor comprising the polymer, an oil composition containing the lubricating oil additive, an oil composition containing the viscosity index improver, and an oil composition containing the friction inhibitor. do.
• At least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit is added to the main chain (a) made of a polymer containing a conjugated diene unit.
• a conjugated diene-based graft polymer to which a side chain (b) made of a polymer containing It was found that a viscosity index improver comprising a conjugated diene-based graft polymer has a high viscosity index, and that a friction inhibitor comprising the above-mentioned conjugated diene-based graft polymer has a good friction reducing effect.
• a lubricating oil additive comprising the above conjugated diene-based graft polymer is useful for lubricating oil, and have completed the present invention.
• the side chain (b) binds to an atom contained in a monomer unit that becomes a branched portion contained in the main chain (a),
• the main chain (a) has a number average molecular weight of 5,000 or more, A conjugated diene-based graft polymer having a hydroxyl group bonded to the main chain (a).
• the atom bonded to the side chain (b) contained in the monomer unit serving as the branched portion is not a heteroatom, Any one of [1] to [6], wherein the linking portion containing an atom that binds to the side chain (b) contained in the monomer unit that becomes the branched portion is not an aromatic group derived from an aromatic vinyl compound.
• (A-1) A step of lithiating anion active sites contained in the polymer (M) by reacting the polymer (M) containing a conjugated diene unit with an organolithium compound in the presence of a polar compound.
• A-2) adding a functionalizing agent to functionalize a portion of the lithiated anion active sites;
• B) adding at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound to polymerize from the remaining lithiated anionic active sites in the polymer (M) to obtain a main chain A step of forming a side chain on the polymer (M) to produce a conjugated diene-based graft polymer; and (D) a step of recovering the obtained conjugated diene-based graft polymer;
• the method for producing a conjugated diene-based graft polymer according to any one of [1] to [7].
• step (A-2) (A-3) adding a Lewis acid;
• a step of reacting with a functional group-modified conjugated diene-based polymer having an epoxy group to prepare a conjugated diene-based graft polymer;
• step (C) The conjugated diene-based graft according to [8] or [10], including a step of hydrogenating at least part of the carbon-carbon double bonds contained in the conjugated diene units in the conjugated diene-based graft polymer.
• a method for producing a polymer [12] A lubricating oil additive comprising the conjugated diene-based graft polymer according to any one of [1] to [7]. [13] A viscosity index improver comprising the conjugated diene graft polymer according to any one of [1] to [7].
• a friction inhibitor comprising the conjugated diene graft polymer according to any one of [1] to [7].
• An oil composition comprising a base oil and the lubricating oil additive according to [12].
• An oil composition comprising a base oil and the viscosity index improver according to [13].
• An oil composition comprising a base oil and the friction inhibitor of [14].
• a conjugated diene-based graft polymer having a high viscosity index and a good friction-reducing effect a lubricating oil additive comprising the conjugated diene-based graft polymer, and a viscosity index comprising the conjugated diene-based graft polymer
• An improver, a friction inhibitor comprising the conjugated diene-based graft polymer, an oil composition containing the lubricating oil additive, an oil composition containing the viscosity index improver, and an oil composition containing the friction inhibitor are provided. be done.
• the conjugated diene-based graft polymer of the present invention has a main chain (a) made of a polymer containing a structural unit derived from a conjugated diene (hereinafter also referred to as a conjugated diene unit), and a conjugated diene unit and an aromatic vinyl compound.
• a conjugated diene unit a polymer containing a structural unit derived from a conjugated diene (hereinafter also referred to as a conjugated diene unit), and a conjugated diene unit and an aromatic vinyl compound.
• the side chain (b) binds to an atom contained in a monomer unit that becomes a branched portion contained in the main chain (a),
• the main chain (a) has a number average molecular weight of 5,000 or more, A hydroxyl group is bonded to the main chain (a).
• the term "graft polymer” refers to a polymer having a backbone composed of a polymer chain and side chains composed of a polymer chain as branches.
• the body unit and the monomer unit that constitutes the side chain polymer chain may be the same or different.
• the conjugated diene-based graft polymer of the present invention has a main chain (a) composed of a polymer containing conjugated diene units.
• the main chain contained in the conjugated diene-based graft polymer of the present invention refers to the entire polymer chain composed of all monomer units including the conjugated diene units constituting the main chain.
• a method of lithiating the main chain by reacting a pre-synthesized conjugated diene-based polymer described later with an organic alkali metal compound in the presence of tetramethylethylenediamine, and then polymerizing a monomer that becomes the structural unit of the side chain.
• conjugated diene-based polymer portion synthesized in advance.
• the conjugated diene-based polymer synthesized in advance contains a structural unit (butadiene unit) derived from butadiene with a vinyl bond, it is bonded to a carbon atom in the polymer skeleton (-(C-C) n -).
• the main chain (a) contains a conjugated diene unit as a monomer unit constituting the polymer.
• conjugated dienes include butadiene, isoprene, farnesene, myrcene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1 ,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, and conjugated dienes such as chloroprene.
• conjugated diene butadiene, isoprene, farnesene and myrcene are preferred, butadiene and isoprene are more preferred, and butadiene is even more preferred.
• the conjugated diene to be the conjugated diene unit may be used alone or in combination of two or more.
• the main chain (a) is preferably composed of conjugated diene units in an amount of 40% by mass or more among all the monomer units constituting the polymer.
• the total content of conjugated diene units is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total monomer units of the main chain (a).
• the main chain (a) comprises at least one monomer selected from the group consisting of butadiene units and isoprene-derived structural units (isoprene units) in at least 40% by mass of the total monomer units constituting the polymer. In one embodiment, it is preferably a body unit.
• the total content of butadiene units and isoprene units is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total monomer units constituting the main chain (a).
• Examples of monomer units other than butadiene units and isoprene units contained in the main chain (a) include conjugated diene units other than the above-mentioned butadiene units and isoprene units, aromatic vinyl compound units, and the like.
• aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2- Examples include vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene.
• aromatic vinyl compounds styrene, 4-methylstyrene and ⁇ -methylstyrene are preferred, and styrene and ⁇ -methylstyrene are more preferred.
• the aromatic vinyl compound to be the aromatic vinyl compound unit may be used alone or in combination of two or more.
• the content of monomer units other than butadiene units and isoprene units in the main chain (a) is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.
• the aromatic vinyl compound unit is less than the above range, the resulting lubricating oil additive (viscosity index improver, friction inhibitor) tends to be improved in shear stability.
• the resulting conjugated diene-based graft polymer tends to be improved in processability.
• the number average molecular weight (Mn) of the main chain (a) is 5,000 or more, preferably 6,000 or more, more preferably 7,000 or more, still more preferably 10,000 or more, and particularly preferably 20,000 or more. . Also, it is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less.
• Mn of the main chain (a) is, for example, a side chain after lithiating the main chain by reacting a previously synthesized conjugated diene-based polymer described later with an organic alkali metal compound in the presence of tetramethylethylenediamine.
• Mn of a conjugated diene-based polymer synthesized in advance which is a constituent element of the main chain.
• the Mn of the main chain (a) is within the above range, when the conjugated diene-based graft polymer is produced by the production method of the present invention, the processability during production is excellent and the economy is favorable. There is a tendency. In addition, it tends to be excellent in the viscosity index and friction reducing effect of the conjugated diene-based graft polymer.
• Mn is the number average molecular weight in terms of standard polystyrene obtained from measurement by gel permeation chromatography (GPC).
• the conjugated diene-based graft polymer used in the present invention may be a polymer hydrogenated by a method such as the hydrogenation step described later.
• the Mn in the main chain (a) means the Mn before hydrogenation.
• the vinyl content of the main chain (a) is preferably 90 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less.
• the vinyl content of the main chain (a) is preferably 0.5 mol % or more, more preferably 1 mol % or more.
• the "vinyl content" refers to 1,2-bonds, 3,4-bonds (other than farnesene), and 3,13- of conjugated diene units (conjugated diene units other than 1,4-bonds (other than farnesene) and 1,13-bonds (for farnesene)) means total mol %.
• the vinyl content of the polymer is defined as the vinyl content obtained from the bonding form of the conjugated diene units contained in the polymer before hydrogenation.
• Vinyl content is derived from conjugated diene units linked by 1,2-linkages, 3,4-linkages (for non-farnesene), and 3,13-linkages (for farnesene) using 1 H-NMR. is calculated from the area ratio of the peak derived from the 1,4-bond (other than farnesene) and 1,13-bond (farnesene) conjugated diene unit.
• the vinyl content of the main chain (a) can be designed according to the purpose.
• the obtained conjugated diene-based graft polymer tends to be excellent in fluidity and low-temperature properties.
• the resulting conjugated diene-based graft polymer tends to have excellent reactivity.
• the main chain (a) is composed only of butadiene units, and at least part of the carbon-carbon double bonds contained in the butadiene units are hydrogenated conjugated diene-based graft polymers, and the Mn is relatively When large (e.g., when Mn is about 10,000 or greater), a vinyl content of 25 mol % or greater is preferred to prevent performance degradation due to crystallization after hydrogenation.
• the vinyl content of the main chain (a) can be determined, for example, by reacting a previously synthesized conjugated diene polymer described later with an organic alkali metal compound in the presence of tetramethylethylenediamine to lithiate the main chain, followed by In the case of production by a method of polymerizing a monomer that becomes the structural unit of, the type of solvent used in producing the pre-synthesized conjugated diene polymer that will be the constituent of the main chain (a), if necessary A desired value can be obtained by controlling the polar compound used, the polymerization temperature, and the like.
• the glass transition temperature (Tg) of the main chain (a) depends on the vinyl content of the conjugated diene unit in the polymer chain that becomes the main chain (a), the type of the conjugated diene unit, and the content of monomer units other than the conjugated diene unit. Although it may vary depending on the content and the like, -150 to 50°C is preferred, -130 to 50°C is more preferred, and -130 to 30°C is even more preferred. When the Tg is within the above range, for example, it is possible to prevent the viscosity from increasing, which facilitates handling. In the present invention, Tg is the peak top value of DDSC obtained by differential scanning calorimetry (DSC) measurement.
• DSC differential scanning calorimetry
• the conjugated diene-based graft polymer of the present invention has a side chain (b) comprising a polymer containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units.
• the side chain (b) contains at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units as monomer units constituting the polymer.
• conjugated diene that can constitute the monomer unit of the side chain (b) are the same as the specific examples of the conjugated diene that constitutes the monomer unit of the main chain (a).
• conjugated dienes that become the conjugated diene units contained in the side chain (b) butadiene, isoprene, farnesene and myrcene are preferred, and butadiene and isoprene are more preferred.
• the conjugated diene to be the conjugated diene unit may be used alone or in combination of two or more.
• aromatic vinyl compound that can constitute the monomer units of the side chain (b) are the same as the specific examples of the aromatic vinyl compound that can constitute the monomer units of the main chain (a).
• aromatic vinyl compounds styrene and ⁇ -methylstyrene are preferred.
• the aromatic vinyl compound to be the aromatic vinyl compound unit may be used alone or in combination of two or more.
• the side chain (b) is selected from the group consisting of homopolymers, conjugated diene units, and aromatic vinyl compound units, in which the backbone of the polymer chain consists of only one type of conjugated diene unit or one type of aromatic vinyl compound unit.
• the polymer constituting the side chain (b) may be of one type alone, or may be of two or more types having different structures.
• the content of the conjugated diene unit contained in the polymer constituting the side chain (b) is preferably 50% by mass or more, and 70% by mass or more, based on the total monomer units of the side chain (b). More preferably, it is particularly preferably 80% by mass or more, and may be 100% by mass.
• the resulting conjugated diene-based graft polymer for example, when used as a lubricating oil additive (viscosity index improver, friction inhibitor), is used as a lubricating oil additive (Viscosity index improver, friction inhibitor) tends to improve shear stability.
• the conjugated diene that can constitute the side chain (b) preferably contains at least one selected from the group consisting of butadiene and isoprene.
• the total content of butadiene units and isoprene units contained in the polymer constituting the side chain (b) is preferably 50% by mass or more, preferably 70% by mass, of the total monomer units constituting the polymer. % or more, particularly preferably 80 mass % or more, and may be 100 mass %.
• the mass ratio of butadiene units and isoprene units (butadiene units/isoprene units) contained in the side chain (b) is preferably in the range of 0/100 to 50/50, more preferably in the range of 0/100 to 30/70.
• a range of 0/100 to 20/80 is particularly preferred.
• the obtained conjugated diene graft polymer can be used, for example, as a lubricating oil additive (viscosity When used as an index improver, friction inhibitor), there tends to be an excellent balance between the thickening effect of lubricating oil additives (viscosity index improver, friction inhibitor) and low-temperature properties.
• the content of the aromatic vinyl compound unit contained in the polymer constituting the side chain (b) is preferably 50% by mass or less, preferably 30% by mass, of the total monomer units constituting the polymer. It is more preferably 20% by mass or less, particularly preferably 20% by mass or less, and may be 0% by mass.
• a lubricating oil additive viscosity index improver, friction inhibitor
• lubricating oil Shear stability of additives viscosity index improvers, friction inhibitors
• the number average molecular weight (Mn) of the side chain (b) is preferably 500 or more and 300,000 or less, more preferably 1,000 or more and 200,000 or less, and 1,000 or more and 150,000 or less. More preferred.
• the Mn of the side chain (b) is, for example, a conjugated diene-based polymer synthesized in advance described later, which is lithiated by reacting the main chain with an organic alkali metal compound in the presence of tetramethylethylenediamine.
• the conjugated diene-based graft polymer obtained in the present invention may be a polymer hydrogenated by a method such as the hydrogenation step described later.
• the Mn of the side chain (b) is the Mn before hydrogenation.
• the vinyl content of the side chain (b) is preferably 99 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.
• the vinyl content of the side chain (b) is preferably 0.5 mol % or more, more preferably 1 mol % or more.
• the vinyl content of the side chain (b) can be determined, for example, by reacting a conjugated diene-based polymer synthesized in advance, which will be described later, with an organic alkali metal compound in the presence of tetramethylethylenediamine to lithiate the main chain, and then determining the structure of the side chain.
• the vinyl content of the conjugated diene-based graft polymer calculated from the 1 H-NMR spectrum, the vinyl content of the main chain (a) described above, and the main chain can be calculated from the charge ratio of the monomers that are the raw materials of the monomer units that constitute the side chain.
• the lubricating oil additive viscosity index improver, friction inhibitor
• the polymer to be the side chain (b) is composed only of butadiene units, and the carbon-carbon double bond contained in the butadiene units is a conjugated diene-based graft polymer in which at least part of the carbon double bonds are hydrogenated.
• Mn is relatively high (eg, Mn is about 10,000 or greater)
• a vinyl content of 25 mol % or greater is preferred to prevent performance degradation due to crystallization after hydrogenation.
• the vinyl content of the side chain (b) can be determined, for example, by reacting a conjugated diene-based polymer synthesized in advance, which will be described later, with an organic alkali metal compound in the presence of tetramethylethylenediamine to lithiate the main chain, followed by
• the polymerization temperature A desired value can be obtained by controlling such as.
• the glass transition temperature (Tg) of the side chain (b) depends on the vinyl content of the conjugated diene unit in the polymer chain that becomes the side chain (b), the type of conjugated diene, and the content of monomer units other than the conjugated diene unit. Although it may vary depending on the amount and the like, -150 to 50°C is preferred, -130 to 50°C is more preferred, and -130 to 30°C is even more preferred. When the Tg is within the above range, for example, it is possible to prevent the viscosity from increasing, which facilitates handling.
• the side chain (b) may be a block copolymer chain containing a polymer block (b1) containing an aromatic vinyl compound unit and a polymer block (b2) containing a conjugated diene unit.
• the polymer block (b1) contains aromatic vinyl compound units. Specific examples and preferred examples of the aromatic vinyl compound unit are the same as specific examples and preferred examples of the aromatic vinyl compound unit constituting the monomer unit of the side chain (b).
• the content of the aromatic vinyl compound unit is preferably more than 70 mol%, more preferably more than It is 80 mol % or more, more preferably 90 mol % or more, still more preferably 95 mol % or more, and particularly preferably substantially 100 mol %.
• the polymer block (b1) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter referred to as "another unsaturated monomer unit") as long as it does not interfere with the object and effect of the present invention. may be contained in the polymer block (b1) in a proportion of 30 mol% or less, preferably less than 20 mol%, more preferably less than 15 mol%, still more preferably less than 10 mol% , more preferably less than 5 mol %, particularly preferably 0 mol %.
• Examples of other unsaturated monomers include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, myrcene, farnesene, isobutylene, methyl methacrylate, methyl vinyl ether, ⁇ - At least one selected from the group consisting of pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran and the like.
• the bonding form is not particularly limited, and may be random or tapered.
• the Mn of the polymer block (b1) is not particularly limited, but the Mn of the polymer block (b1) is preferably 500 to 300,000, More preferably from 1,000 to 200,000, still more preferably from 1,000 to 50,000.
• the polymer block (b1) in which the side chain (b) of the conjugated diene-based graft polymer has an Mn within the above range properties such as shear stability of the oil composition containing the conjugated diene-based graft polymer tend to improve.
• the content of the polymer block (b1) in the conjugated diene-based graft polymer is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, 40% by mass or less is particularly preferred.
• the content of the polymer block (b1) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
• the content of the polymer block (b1) is at least the above lower limit, the production of the conjugated diene-based graft polymer tends to be easy.
• the content of the polymer block (b1) in the conjugated diene graft polymer can be determined by 1 H-NMR measurement.
• polymer blocks (b1) When the side chain (b) is the block copolymer chain, it should contain at least one polymer block (b1).
• the block copolymer chain contains two or more polymer blocks (b1), the polymer blocks (b1) may be the same or different.
• the polymer blocks (b1) contained in these two or more copolymer chains may be the same or different. good.
• “polymer blocks are different” means the monomer units constituting the polymer blocks, Mw, stereoregularity, and, in the case of having a plurality of monomer units, the ratio of each monomer unit and the form of copolymerization. It means that at least one of (random, gradient, block) is different.
• the contained polymer block (b2) contains a conjugated diene compound unit.
• the content of the conjugated diene unit in the polymer block (b2) is preferably 50 mol% or more, more preferably 70 mol% or more, from the viewpoint of improving the properties of the oil composition containing the conjugated diene-based graft polymer to be obtained. , more preferably 90 mol % or more, and particularly preferably substantially 100 mol %.
• the specific examples and preferred examples of the conjugated diene and the content and preferred ratio of each monomer are the specific examples and preferred examples of the conjugated diene constituting the monomer unit of the side chain (b) and each monomer. is the same as the content and preferred ratio of
• the polymer blocks (b2) may be the same or different.
• the polymer blocks (b2) contained in these two or more copolymer chains may be the same or different.
• the vinyl content of the conjugated diene units of the polymer block (b2) is preferably 1 to 60 mol%, more preferably 2 to 40 mol%, still more preferably 3 to 30 mol%, particularly preferably 4 ⁇ 20 mol%.
• the vinyl content of the polymer block or polymer chain is determined by the type of solvent used, the polar compound used as necessary, A desired value can be obtained by controlling the polymerization temperature and the like.
• the polymer block (b2) may contain structural units derived from monomers other than the conjugated diene compound as long as the objects and effects of the present invention are not hindered.
• the content of structural units derived from monomers other than the conjugated diene compound is preferably less than 50 mol%, more preferably less than 30 mol%, still more preferably 20 It is less than mol %, even more preferably less than 10 mol %, and particularly preferably 0 mol %.
• Examples of other monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, and N-vinylcarbazole.
• aromatic vinyl compounds such as vinylnaphthalene and vinylanthracene, and methyl methacrylate, methyl vinyl ether, ⁇ -pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, At least one compound selected from the group consisting of 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene and the like is preferably included.
• the Mn of the polymer block (b2) is not particularly limited. From the point of view, Mn of the polymer block (b2) is preferably 500 to 300,000, more preferably 1,000 to 200,000, still more preferably 1,000 to 50,000.
• the side chain (b) is the block copolymer chain, it should have at least one polymer block (b2).
• the block copolymer chain has two or more polymer blocks (b2)
• the polymer blocks (b2) may be the same or different.
• the polymer blocks (b2) contained in these two or more copolymer chains may be the same or different. good.
• the block copolymer chain may include polymer blocks other than the above polymer blocks (b1) and (b2) as long as the object and effect of the present invention are not hindered. may contain polymer blocks composed of other monomers.
• the side chain (b) contains the block copolymer chain
• the total content of the polymer block (b1) and the polymer block (b2) with respect to the entire side chain (b) is 90% by mass. It is preferably at least 95% by mass, more preferably at least 95% by mass, and particularly preferably substantially 100% by mass. If it is 90% by mass or more, the physical properties of the obtained oil composition containing the conjugated diene-based graft polymer tend to be improved.
• the form of bonding is limited as long as the block copolymer chain contains the polymer block (b1) and the polymer block (b2). may be linear, branched, radial, or a combination of two or more of these. Further, these polymer blocks may be directly bonded to each other, or may be indirectly bonded via another polymer block. Among these, the form of bonding between the polymer block (b1) and the polymer block (b2) is preferably such that these polymer blocks are directly bonded to form a straight chain. As an example of such a bond type, the polymer block (b1) is represented by b1 and the polymer block (b2) by b2.
• Examples include copolymer chains, pentablock copolymer chains represented by b2-b1-b2-b1-b2 or b1-b2-b1-b2-b1.
• a diblock copolymer chain designated b2-b1 is preferred.
• the conjugated diene-based graft polymer of the present invention comprises a main chain (a) made of a polymer containing a conjugated diene unit, and at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit. comprising a side chain (b) made of a polymer comprising The side chain (b) is bonded to an atom contained in a monomer unit that becomes a branched portion contained in the main chain (a), and the number average molecular weight of the main chain (a) is 5,000 or more, A hydroxyl group is bonded to the main chain (a).
• the main chain (a) of the conjugated diene-based graft polymer of the present invention contains a monomer unit that serves as a branched portion.
• a side chain (b) is bonded to an atom included in the branched portion of the main chain (a).
• the atom attached to the side chain (b) contained in this branched portion is not a heteroatom.
• the atom bonded to the side chain (b) is not a heteroatom means that the atom is not an atom other than a carbon atom and a hydrogen atom, that is, the atom is a carbon atom or a hydrogen atom (
• the atom to which the side chain (b) is attached is actually a carbon atom since it is a branch point).
• the branch point to which the side chain (b) is bonded is the heteroatom itself, it is not preferable because shear stability and thermal stability tend to deteriorate.
• the atom contained in the monomer unit that becomes the branched portion and the bond with the side chain (b) refers to the atom that constitutes the monomer unit that becomes the branched portion in the main chain (typically a carbon atom ) and the atom constituting the side chain (b) are bound.
• a method for bonding the atoms contained in the monomer units that form the branched portion to the side chain (b) will be described in detail below as an example of a method for producing a conjugated diene-based graft polymer.
• a site containing a carbon atom having anionic activity (hereinafter, a site containing a carbon atom having anionic activity is also referred to as an anion active site) contained in a monomer unit that becomes a branched portion of the polymer a).
• MI method a method of addition-polymerizing a monomer to form a side chain (b), or a functional group-modified polymer that becomes the main chain (a).
• a method (coupling method (CP method)) of reacting an epoxy group contained in a monomer unit serving as a branching portion with an active terminal of a polymer obtained by polymerizing a monomer serving as a structural unit of a side chain, and the like. be done.
• the atoms bonded to the side chain (b) contained in the monomer units that form the branched portion are not heteroatoms.
• the branch point itself at which the main chain and the side chain are bonded is a hetero atom, it is not preferable because the shear stability and thermal stability tend to deteriorate.
• the graft polymer described in Patent Document 2 is prepared by preparing a mixture of a polymer having two active terminals that constitute the main chain and a polymer having one active terminal that constitutes the side chain. , is synthesized by adding a coupling agent containing a silicon atom having 3 or more reactive sites to this mixture and allowing it to react.
• a heteroatom such as a silicon atom derived from the coupling agent serves as a branching point connecting the main chain and the side chain.
• the applicant of the present application modified a polymer that was synthesized in advance as a constituent of the main chain with a compound containing a silicon atom to obtain a functional group-modified polymer, and this functional group-modified polymer and
• An application has been filed for a technique relating to a method for synthesizing a graft polymer by a method of reacting an active terminal of a polymer obtained by polymerizing a monomer that constitutes a structural unit of a side chain.
• a heteroatom such as a silicon atom derived from this functional group-modified polymer serves as a branching point that connects the main chain and the side chain.
• the main chain (a) branch point is an atom (typically a carbon atom) that is not a hetero atom, and the atom is directly bonded to the side chain (b). ing. Therefore, in the conjugated diene-based graft polymer of the present invention, the branch point (connecting point) where the main chain and the side chain are bonded is not a heteroatom, unlike the polymer described above.
• the connecting portion containing the atom that binds to the side chain (b) contained in the monomer unit that becomes the branched portion contained in the main chain (a) is an aromatic vinyl compound. It is a preferred embodiment that it is not an aromatic group derived from.
• the aromatic group is an aromatic ring other than CH 2 ⁇ CR (R is hydrogen, an optionally substituted alkyl group, or an optionally substituted aryl group) possessed by the aromatic vinyl compound.
• the linking portion containing the atom that bonds to the side chain (b) is not an aromatic group derived from an aromatic vinyl compound
• the monomer unit itself that becomes the branched portion contained in the main chain is a structural unit derived from a monomer other than an aromatic vinyl compound (e.g., a conjugated diene), or the unit that becomes the branched portion contained in the main chain Even if the monomer unit itself is an aromatic vinyl compound unit, it means that the side chain (b) is not bound to an atom in the aromatic group of the aromatic vinyl compound. A specific example will be described below.
• a site containing a carbon atom having an anionic activity contained in a monomer unit that becomes a branched portion of a polymer that becomes the main chain (a) described later is lithiated, and the lithiated site having an anionic activity is used as a starting point
• the aromatic vinyl compound contained in the polymer that becomes the main chain (a) has, for example, high anionic activity
• the methyl group portion derived from 4-methylstyrene has high reactivity, and the carbon atom portion of this methyl group has a side chain ( b) is combined.
• styrene unit a structural unit (styrene unit) derived from styrene that serves as the skeleton of the main chain (a) is The side chain (b) is attached to the portion of CH 2 adjacent to the CH to which the carbon atom of the benzene ring is attached in the (—CH 2 —CH—) moiety.
• the side chain (b) is not bonded to the styrene-derived benzene ring, and the linking portion containing the atom bonded to the side chain (b) in the branched portion included in the main chain (a) is This means that it is not an aromatic group derived from an aromatic vinyl compound.
• the linking portion containing the atom that binds to the side chain (b) included in the monomer unit serving as the branched portion included in the main chain (a) is an aromatic It is preferably not an aromatic group derived from a group vinyl compound.
• the linking portion is the above aromatic group, the shear stability and thermal stability are deteriorated.
• the graft polymer described in Journal of Polymer Science: Part A: Polymer Chemistry, 2007, 45, 3513 or Japanese Patent No. 5508066 is a macromonomer (a polymer obtained by polymerizing a monomer that becomes a structural unit of a side chain).
• a macromonomer obtained by directly reacting an aromatic vinyl compound having a polymerizable functional group other than CH 2 ⁇ C— bonded to an aromatic group at the active end of the coalescence
• a monomer that forms the structural unit of the main chain synthesized by the method of polymerizing Derived from this macromonomer, the linking portion that binds to the side chain (b) contained in the branched portion in the main chain (a) becomes an aromatic group.
• the side chain (b) contained in the branched portion in the main chain (a) is bonded.
• a linking moiety is not an aromatic group.
• the average number of side chains (b) per molecule of the conjugated diene-based graft polymer is preferably 2 or more, more preferably 4 or more, and even more preferably 5 or more.
• the average number of side chains (b) per molecule of the conjugated diene-based graft polymer is determined, for example, by reacting a previously synthesized conjugated diene-based polymer described later with an organic alkali metal compound in the presence of tetramethylethylenediamine to obtain a main chain.
• the organic alkali metal used in the lithiation reaction and the conjugated diene polymer to be the structural unit of the main chain are calculated from the charging ratio (molar ratio) of the functionalizing agent added as necessary.
• the conjugated diene-based graft polymer of the present invention preferably has a side chain density of the side chain (b) of 1.0 mol% or more, more preferably 2.0 mol% or more, and 3.0 mol% or more. mol % or more is more preferable, and 4.0 mol % or more is even more preferable.
• the side chain density of the conjugated diene-based graft polymer is less than 1.0 mol%
• a lubricating oil additive viscosity index improver, friction inhibitor
• the shear stability of lubricating oil additives tends to decrease, and the fluidity of conjugated diene-based graft polymers decreases, resulting in poor balance between workability and mechanical properties.
• the side chain density of the side chain (b) is defined as the average number of the side chain (b) per molecule of the conjugated diene graft polymer and the number average molecular weight (Mn ) to obtain from the following formula (1).
• the above side chain density is the number of side chains (b) per molecule of the conjugated diene graft polymer with respect to the total number of monomer units, assuming that the main chain polymer is all styrene units. Means the ratio of the average number of threads.
• (Side chain density) (average number of side chains (b) per molecule of conjugated diene graft polymer)/[(number average molecular weight Mn of main chain (a))/(molecular weight of styrene unit)] x 100 (1)
• the Mn of the main chain (a) is obtained by, for example, lithiating the main chain by reacting a previously synthesized conjugated diene-based polymer described later with an organic alkali metal compound in the presence of tetramethylethylenediamine, followed by lithiation of the side chain.
• Mn in terms of standard polystyrene of a conjugated diene-based polymer synthesized in advance to be a constituent element of the main chain.
• the conjugated diene-based graft polymer of the present invention has hydroxyl groups bonded to the main chain (a).
• the hydroxyl group is bonded to the main chain (a) directly or through a linking chain.
• "bonded directly to the main chain (a)” means that a hydroxyl group is directly bonded to a monomer unit constituting the polymer that forms the main chain. Bonding to the main chain (a) through the linking chain means that one end of the linking chain is bonded to a monomer unit constituting the polymer that is the main chain, and a hydroxyl group is attached to the other end of the linking chain. It means that they are directly connected.
• the case represented by the following formula (I-1) is the case where the hydroxyl group is directly bonded to the main chain
• the following formula (I- 2) is a case where a hydroxyl group is bonded to the main chain through a linking chain (the following formula (I-1) and the following formula (I-2) show the structure when butadiene is hydrogenated. ing).
• R 1 is a linking chain.
• R 1 is a divalent organic group and is an alkylene group having no heteroatom.
• the connecting chain contains a heteroatom, particularly when a hydroxyl group is directly bonded to the heteroatom, the shear stability and thermal stability of the conjugated diene-based graft polymer deteriorate.
• the average number of hydroxyl groups bonded to the main chain (a) per molecule of the conjugated diene-based graft polymer is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
• the average number of hydroxyl groups bonded to the main chain (a) per molecule of the conjugated diene graft polymer is the hydroxyl value (mgKOH/g) of the conjugated diene graft polymer calculated according to JIS K1557-1:2007. and the standard polystyrene-equivalent number average molecular weight (Mn) of the conjugated diene-based graft polymer according to the following formula (2).
• the obtained conjugated diene-based graft polymer may be used, for example, as a lubricating oil additive (viscosity index improver, friction When used as an inhibitor), it tends to be excellent in the viscosity index and friction reducing effect of lubricating oil additives (viscosity index improver, friction When used as an inhibitor), it tends to be excellent in the viscosity index and friction reducing effect of lubricating oil additives (viscosity index
• the concentration of hydroxyl groups bonded to the main chain (a) is preferably 3.0 mol % or more. mol % or more is more preferable, and 4.0 mol % or more is even more preferable.
• the concentration of hydroxyl groups bonded to the main chain (a) is 3.0 mol% or more, the affinity with polar materials tends to be excellent, and the resulting conjugated diene-based graft polymer can be used, for example, as a lubricant additive (viscosity When used as an index improver, friction inhibitor), it tends to be excellent in viscosity index and friction reduction effect of lubricating oil additives (viscosity index improver, friction inhibitor).
• the concentration of hydroxyl groups bonded to the main chain (a) is preferably 100 mol % or less, more preferably 80 mol % or less, and even more preferably 60 mol % or less.
• the concentration of hydroxyl groups bonded to the main chain (a) is 100 mol % or less, the affinity with non-polar materials and the solubility in base oils tend to be excellent.
• the concentration of hydroxyl groups bonded to the main chain (a) is the average number of hydroxyl groups bonded to the main chain (a) per molecule of the conjugated diene graft polymer and the standard polystyrene conversion of the main chain (a). It calculates
• the Mn of the main chain (a) is obtained by, for example, lithiating the main chain by reacting a previously synthesized conjugated diene-based polymer described later with an organic alkali metal compound in the presence of tetramethylethylenediamine, followed by lithiation of the side chain.
• Mn in terms of standard polystyrene of a conjugated diene-based polymer synthesized in advance to be a constituent element of the main chain.
• the combination of the main chain (a) polymer and side chain (b) polymer contained in the conjugated diene-based graft polymer is not particularly limited, and may be the same or different, and is designed according to the purpose. It is possible.
• the fact that the polymer forming the main chain (a) and the polymer forming the side chain (b) are different means that at least one selected from the group consisting of (i) to (iv) below is different.
• the molecular weight of the polymer that forms the main chain (a) is different from the molecular weight of the polymer that forms the side chain (b).
• the type or combination of types of monomer units in the polymer that forms the main chain (a) is different from the type or combination of types of monomer units in the polymer that forms the side chain (b).
• the monomer unit composition ratio of the polymer that becomes the main chain (a) is side It differs from the monomer unit composition ratio of the polymer that forms the chain (b).
• the vinyl content of the conjugated diene unit of the polymer that becomes the main chain (a) is the same as that of the side chain (b). different from the vinyl content of the conjugated diene units of the polymer.
• the conjugated diene-based graft polymer of the present invention 50% by mass or more of the total monomer units constituting the polymer is at least one monomer unit selected from the group consisting of butadiene units and isoprene units. is a preferred embodiment.
• the total content of butadiene units and isoprene units is more preferably 60 to 100% by mass, more preferably 70 to 100% by mass, based on the total monomer units of the conjugated diene graft polymer.
• the content of monomer units other than butadiene units and isoprene units in the conjugated diene-based graft polymer of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass. More preferred are:
• the obtained conjugated diene graft polymer is used as, for example, a lubricating oil additive (viscosity index improver, friction inhibitor). Improver, friction inhibitor) tends to improve shear stability, and conjugated diene-based graft polymer tends to improve processability.
• the conjugated diene-based graft polymer used in the present invention at least part of the carbon-carbon double bonds contained in the conjugated diene units of the polymer may be hydrogenated or may be in a non-hydrogenated state.
• the conjugated diene-based graft polymer used in the present invention is a conjugated diene in which at least part of the carbon-carbon double bonds contained in the conjugated diene units of the polymer are hydrogenated.
• a system graft polymer is one preferred embodiment.
• the carbon-carbon double bonds contained in the conjugated diene units in the conjugated diene-based graft polymer are preferably hydrogenated at 50 mol% or more, more preferably at 60 mol% or more.
• the hydrogenation rate is usually 100 mol % or less.
• the hydrogenation rate (hydrogenation rate) may be substantially 100 mol % (that is, substantially complete hydrogenation).
• the thermal stability and shear stability of the lubricating oil additive (viscosity index improver, friction inhibitor) comprising the conjugated diene graft polymer tend to be improved.
• the degree of hydrogenation is obtained by calculating the content of carbon-carbon double bonds contained in the conjugated diene units in the polymer before and after hydrogenation using 1 H-NMR, and then obtaining these contents. value.
• the weight average molecular weight (Mw) of the conjugated diene-based graft polymer of the present invention is preferably 5,000 or more and 2,000,000 or less, preferably 10,000 or more and 1,500,000 or less, 15,000 or more and 1,000,000 or less are more preferable.
• Mw of the conjugated diene-based graft polymer is within the above range, when the obtained conjugated diene-based graft polymer is used as, for example, a lubricating oil additive (viscosity index improver, friction inhibitor), the lubricating oil additive (viscosity Index improver, friction inhibitor) tend to have an excellent balance between the thickening effect and shear stability, and also tend to be excellent in process passability during production and tend to be economical.
• the molecular weight distribution (Mw/Mn) of the conjugated diene-based graft polymer of the present invention is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, even more preferably 1.0 to 5.0. 1.0 to 2.0 is particularly preferred.
• Mw/Mn is within the above range, variation in viscosity of the conjugated diene-based graft polymer is small, which is more preferable.
• Mn means number average molecular weight
• Mn is the number average molecular weight in terms of standard polystyrene obtained from GPC measurement.
• the molecular weight distribution (Mw/Mn) means the ratio (Mw/Mn) of the weight average molecular weight (Mw) converted to standard polystyrene and the number average molecular weight (Mn) obtained by GPC measurement.
• the vinyl content of the conjugated diene-based graft polymer of the present invention is preferably 99 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.
• the vinyl content of the conjugated diene-based graft polymer is preferably 0.5 mol % or more, more preferably 1 mol % or more.
• the vinyl content of the conjugated diene-based graft polymer is within the above range, when the resulting conjugated diene-based graft polymer is used as, for example, a lubricating oil additive (viscosity index improver, friction inhibitor), it can be used as a lubricating oil additive ( Viscosity index improver, friction inhibitor) tends to have an excellent balance between thickening effect and low temperature properties.
• the conjugated diene-based graft polymer is composed only of butadiene units, and at least part of the carbon-carbon double bonds contained in the butadiene units are hydrogenated.
• the vinyl content is reduced to 25 to prevent performance deterioration due to crystallization after hydrogenation.
• mol % or more is preferable.
• the glass transition temperature (Tg) of the conjugated diene-based graft polymer depends on butadiene units, isoprene units and butadiene units, the vinyl content of conjugated diene units other than isoprene units, the type of conjugated diene units, and the amount of other monomers other than conjugated diene units. Although it may vary depending on the content of body units and the like, -150 to 50°C is preferred, -130 to 50°C is more preferred, and -130 to 30°C is even more preferred. When the Tg is within the above range, for example, it is possible to prevent the viscosity from increasing, which facilitates handling.
• the mass ratio of the main chain and side chains in the conjugated diene-based graft polymer of the present invention is preferably in the range of 1/99 to 90/10, more preferably in the range of 3/97 to 80/20, and 5/95 to 70. A range of /30 is more preferred. When the mass ratio of the main chain to the side chains is within the above range, the processability of the conjugated diene-based graft polymer tends to be improved.
• the total amount of catalyst residues derived from the polymerization catalyst, hydrogenation catalyst (hydrogenation catalyst), etc. used for its production is preferably in the range of 0 to 500 ppm in terms of metal.
• an organic alkali metal such as an organic lithium compound as described later
• an alkali metal such as lithium is included.
• nickel and aluminum are included when a Ziegler-based catalyst described later is used as a catalyst in the hydrogenation reaction.
• the amount of the catalyst residue is within the above range, the tackiness does not decrease during processing, etc., and the heat resistance of the conjugated diene-based graft polymer obtained by the present invention is improved.
• the total amount of catalyst residue in the conjugated diene-based graft polymer is more preferably 0 to 300 ppm, more preferably 0 to 200 ppm in terms of metal.
• the catalyst residue amount can be measured by using, for example, an inductively coupled plasma mass spectrometer (ICP-MS) or a polarized Zeeman atomic absorption spectrophotometer.
• a method for adjusting the catalyst residue amount of the conjugated diene-based graft polymer to such a specific amount there is a method of purifying the conjugated diene-based graft polymer and sufficiently removing the catalyst residue.
• a purification method washing with water or hot water, an acidic aqueous solution, or an organic solvent typified by methanol, acetone, etc., or washing with a supercritical fluid carbon dioxide is preferable. Cleaning efficiency can be further enhanced by using an acidic aqueous solution for cleaning.
• Acids used include, for example, monovalent or polyvalent strong acids such as hydrochloric acid, nitric acid, and sulfuric acid; monovalent or polyvalent carboxylic acids such as acetic acid, propionic acid, succinic acid, and citric acid; Or polyvalent weak acids are preferred.
• the number of washings is preferably from 1 to 20 times, more preferably from 1 to 10 times, from an economical point of view.
• the washing temperature is preferably 20 to 100°C, more preferably 40 to 90°C.
• the necessary amount of the polymerization catalyst can be reduced.
• the catalyst residue amount can be reduced.
• a conjugated diene-based graft polymer synthesized in advance is treated with an organic alkali metal compound in the presence of tetramethylethylenediamine.
• a functionalizing agent is added to add hydroxyl groups to some of the lithiation points, and then a monomer that becomes the structural unit of the side chain is polymerized (in this specification, hereinafter referred to as the macroinitiator method), or the epoxy group contained in the monomer unit that becomes the branched portion of the functional group-modified polymer that becomes the main chain (a), and the structural unit of the side chain
• a coupling method A method of reacting an active terminal of a polymer obtained by polymerizing a monomer.
• MI method ⁇ Macro initiator method (MI method)>
• a macroinitiator method (MI method) including the following steps (A-1), (A-2), (B), and (D) is a preferred embodiment.
• Step (A-1) The method for producing the polymer (M) containing a conjugated diene unit that is a constituent of the main chain in the step (A-1) is preferably, for example, an emulsion polymerization method or a solution polymerization method. From the point of view, the solution polymerization method is more preferable.
• the polymer (M) containing conjugated diene units forms the main chain (a) of the conjugated diene-based graft polymer of the present invention.
• conjugated diene which is a monomer unit constituting the polymer (M) containing the conjugated diene unit, and description of the preferred content thereof are given in relation to the main chain (a) of the conjugated diene-based graft polymer. Same as description.
• Examples of monomers other than conjugated dienes that are monomer units constituting the polymer (M) containing conjugated diene units include aromatic vinyl compounds.
• aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N- Diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like.
• aromatic vinyl compounds examples include styrene, ⁇ -methyl
• the content of monomer units other than butadiene units and isoprene units in the polymer (M) containing a conjugated diene unit is preferably 60% by mass or less, more preferably 50% by mass or less, and 40% by mass. % or less is more preferable.
• a lubricating oil additive viscosity index improver, friction inhibitor
• the lubricating oil additive viscosity Index improvers, friction inhibitors
• the resulting conjugated diene-based graft polymer tends to be improved in processability.
• the description of the number average molecular weight (Mn), vinyl content, preferred aspects of Tg, etc. of the polymer (M) containing conjugated diene units is the same as the description of the main chain (a) of the conjugated diene-based graft polymer.
• the emulsion polymerization method which is an example of the method for producing the polymer (M) containing conjugated diene units
• a known method or a method based on a known method can be applied.
• a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in a dispersion medium in the presence of an emulsifier, and emulsion polymerized with a radical polymerization initiator.
• emulsifiers include salts of long-chain fatty acids with 10 or more carbon atoms and rosinates.
• long-chain fatty acid salts include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
• the dispersion medium may contain a water-soluble organic solvent such as methanol or ethanol as long as the stability during polymerization is not impaired.
• radical polymerization initiators include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide.
• a chain transfer agent may be used to adjust the molecular weight of the resulting polymer (M) containing conjugated diene units.
• chain transfer agents include mercaptans such as t-dodecylmercaptan and n-dodecylmercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, ⁇ -terpinene, ⁇ -methylstyrene dimer and the like.
• the temperature for emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator to be used, but it is usually in the range of 0 to 100°C, preferably 0 to 60°C.
• the polymerization mode may be either continuous polymerization or batch polymerization.
• the polymerization reaction can be stopped by adding a polymerization terminator.
• the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
• an anti-aging agent may be added as necessary.
• unreacted monomers are removed from the obtained latex if necessary, and then salts such as sodium chloride, calcium chloride and potassium chloride are used as coagulants, and if necessary nitric acid, sulfuric acid and the like are added.
• the polymer (M) containing the conjugated diene unit is coagulated while adjusting the pH of the coagulation system to a predetermined value by adding an acid, the polymer is recovered by separating the dispersion medium. Then, the polymer (M) containing the conjugated diene unit is obtained by washing with water, dehydration, and drying.
• the latex and an extender oil made into an emulsified dispersion may be mixed in advance, and the polymer (M) containing an oil-extended conjugated diene unit may be recovered.
• the solution polymerization method which is an example of the method for producing the polymer (M) containing conjugated diene units
• a known method or a method based on the known method can be applied.
• a known method or a method based on the known method can be applied.
• a known method or a method based on the known method can be applied in a solvent, using a Ziegler-based catalyst, a metallocene-based catalyst, or an anionically polymerizable active metal or active metal compound as an initiator, optionally in the presence of a polar compound, a monomer containing a conjugated diene Polymerize the body.
• solvents examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as toluene and xylene can be used.
• the initiator is preferably an anionically polymerizable active metal or an active metal compound, more preferably an anionically polymerizable active metal compound.
• anionically polymerizable active metals examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium. . Among these, alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.
• organic alkali metal compound is preferable as the anionically polymerizable active metal compound.
• organic alkali metal compounds include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; , 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; and sodium naphthalene, potassium naphthalene and the like.
• organic lithium compounds are preferred, and organic monolithium compounds are more preferred.
• the amount of the initiator to be used can be appropriately set according to the melt viscosity, molecular weight, etc. of the polymer (M) containing the conjugated diene unit. It is used in an amount of 01 to 3 parts by weight.
• the organic alkali metal compound can be used as an organic alkali metal amide by reacting it with a secondary amine such as dibutylamine, dihexylamine or dibenzylamine. .
• Polar compounds are usually used in anionic polymerizations to adjust the microstructure (vinyl content) of the conjugated diene units without inactivating the reaction.
• polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
• the polar compound is generally used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
• the temperature of solution polymerization is usually in the range of -80 to 150°C, preferably in the range of 0 to 100°C, more preferably in the range of 10 to 90°C.
• the mode of polymerization may be either a batchwise system or a continuous system.
• the polymerization reaction of the above solution polymerization can be terminated by adding a polymerization terminator.
• the polymerization terminator include alcohols such as methanol and isopropanol.
• the obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate a polymer (M) containing a conjugated diene unit, or the polymerization reaction solution is washed with water, separated, and dried to obtain the conjugated diene.
• a polymer (M) containing units can be isolated.
• the polymerization reaction solution after termination of the polymerization may be directly used for the lithiation reaction as long as it does not affect the lithiation reaction.
• the solvent may be partly removed, or the solvent may be added to dilute the polymerization reaction solution.
• the polymer (M) containing conjugated diene units thus obtained may be used as it is for the lithiation reaction, but the carbon-carbon double bond contained in the conjugated diene unit in the conjugated diene polymer may be modified after at least a part of is hydrogenated by the hydrogenation method described below.
• the anion active site contained in the polymer (M) containing the conjugated diene unit obtained as described above is lithiated by reacting it with an organolithium compound in the presence of a polar compound. do. Lithiation under such conditions lithiates the anion active sites, especially the carbon-carbon double bond portion contained in the vinyl bond type conjugated diene unit contained in the polymer (M).
• the skeleton of the main chain (a) of the aromatic vinyl compound unit for example, the styrene unit, which does not have a substituent in the aromatic group having high reactivity with respect to the anion contained in the polymer (M)
• the linking portion containing the atom that bonds to the side chain (b) contained in the monomer unit that becomes the branch portion is not an aromatic group derived from the aromatic vinyl compound. .
• the polymer (M) contains an aromatic vinyl compound unit
• an anion is added to the aromatic vinyl compound unit.
• the aromatic group does not contain a highly active functional group (a functional group highly reactive with the organolithium compound).
• Styrenes having aromatic groups containing such functional groups include 4-methylstyrene, 4-propylstyrene, and the like.
• Examples of the organic lithium compound used for lithiation of the polymer (M) in the step (A-1) include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, organic monolithium compounds such as phenyllithium and stilbenelithium; lithium compounds; Among these organic lithium compounds, organic monolithium compounds are preferred, n-butyllithium and sec-butyllithium are more preferred, and sec-butyllithium is particularly preferred.
• the side chain density is obtained from the following formula (1).
• (Side chain density) (average number of side chains (b) per molecule of conjugated diene graft polymer)/[(number average molecular weight Mn of main chain (a))/(molecular weight of styrene unit)] x 100 (1) That is, the amount of the organolithium compound used is determined so that the desired side chain density and hydroxyl group concentration are obtained by adjusting the number average molecular weight Mn of the main chain (a) and the side chain (b ) and the average number of hydroxyl groups bonded to the main chain (a) can be determined naturally.
• the polar compound used in the lithiation of the polymer (M) in step (A-1) above is used to promote the lithiation reaction.
• polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
• tertiary amines are preferred, and tetramethylethylenediamine is particularly preferred.
• the amount of the polar compound used is preferably 0.01 mol or more, more preferably 0.05 mol or more, and particularly preferably 0.1 mol or more, relative to 1 mol of the organic alkali metal compound.
• the amount of the polar compound used is preferably 100 mol or less, more preferably 50 mol or less, and particularly preferably 10 mol or less, per 1 mol of the organic alkali metal compound.
• the amount of the polar compound used is less than 0.01 mol per 1 mol of the organic alkali metal compound, the reaction rate tends to be poor, and when it exceeds 100 mol, the economy tends to be poor.
• the lithiation in the above step (A-1) is usually carried out with the polymer (M) dissolved in a solvent.
• the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; and benzene. , toluene, and xylene; and ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether.
• the reaction temperature for the lithiation in step (A-1) is preferably 0°C or higher, more preferably 10°C or higher, and particularly preferably 20°C or higher. Also, the temperature is preferably 100° C. or lower, more preferably 80° C. or lower, and particularly preferably 60° C. or lower. If the temperature is less than 0°C, the reaction rate tends to be poor, and if it exceeds 100°C, side reactions such as decomposition tend to increase.
• the reaction time of the lithiation in the step (A-1) can be appropriately set according to the progress of the reaction, preferably 0.01 to 100 hours, more preferably 0.1 to 50 hours, and 0.2 to 20 hours. Time is particularly preferred.
• Step (A-2) In the step (A-2) by the MI method, by reacting a part of the lithiated anion active site obtained in the step (A-1) with a functionalizing agent, the finally obtained conjugated diene system Forms a hydroxyl group that bonds to the main chain (a) of the graft polymer.
• a hydroxyl group is formed by this synthesis method, the hydroxyl group is bonded to the main chain (a) through a linking chain.
• Examples of the functionalizing agent used in the functionalization reaction of the anion active site lithiated in the above step (A-2) include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, and isovaleraldehyde. , n-octylaldehyde, 2-ethylhexylaldehyde, decylaldehyde, dodecylaldehyde, benzaldehyde; and epoxides such as ethylene oxide and propylene oxide.
• aldehydes such as n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, n-octylaldehyde, 2-ethylhexylaldehyde, decylaldehyde, dodecylaldehyde, benzaldehyde are preferred, and 2-ethylhexylaldehyde, Benzaldehyde is particularly preferred.
• the hydroxyl group concentration is obtained from the following formula (3).
• (Hydroxy group concentration) (average number of hydroxyl groups bonded to main chain (a) per molecule of conjugated diene graft polymer)/[(number average molecular weight Mn of main chain (a))/(molecular weight of styrene unit) ] ⁇ 100 (3) That is, the amount of the functionalizing agent used is such that the number average molecular weight Mn of the main chain (a) and the main chain (a) per molecule of the conjugated diene-based graft polymer are combined so as to achieve the desired hydroxyl group concentration. By designing the average number of hydroxyl groups, it can be determined naturally.
• the solvent that can be used in the step (A-2) above is the same as the preferred examples of the solvent in the step (A-1) above. If necessary, a solvent may be further added at any timing after step (A-1).
• the reaction temperature for the functionalization in step (A-2) is preferably 0°C or higher, more preferably 10°C or higher, and particularly preferably 20°C or higher. Moreover, the reaction temperature is preferably 100° C. or lower, more preferably 80° C. or lower, and particularly preferably 60° C. or lower. If the temperature is less than 0°C, the reaction rate tends to be poor, and if it exceeds 100°C, side reactions such as decomposition tend to increase.
• the reaction time of the functionalization in the above step (A-2) can be appropriately set according to the progress of the reaction, preferably 0.01 to 100 hours, more preferably 0.05 to 50 hours, and 0.1 to 20 hours. Time is particularly preferred.
• Step (A-3) In the method for producing a conjugated diene-based graft polymer by the MI method, in order to adjust the vinyl content of the side chain (b) to the desired range, after step (A-1) or step (A-2), (A-3) adding a Lewis acid; It is a preferred embodiment to include
• the Lewis acid is added to reduce the action of the polar compound added to promote the lithiation reaction and to adjust the vinyl content of the side chain in the step (B) described below to the desired range.
• the Lewis acid is preferably an alkyl metal compound that does not deactivate the lithiation point generated in the above step (A-1), such as trimethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutyl.
• Alkylaluminum compounds such as aluminum, tri-n-hexylaluminum, and trioctylaluminum; alkylmagnesium compounds such as butylethylmagnesium, di-n-butylmagnesium, and di-n-hexylmagnesium; dimethyl zinc, Alkyl zinc compounds such as diethyl zinc, di-n-propyl zinc, diisobutyl zinc, and di-n-butyl zinc are included.
• alkylaluminum compounds or alkylzinc compounds are preferred, alkylaluminum compounds are more preferred, and triisobutylaluminum is particularly preferred.
• the amount of the Lewis acid to be used can be appropriately adjusted depending on the vinyl content of the desired side chain (b). is preferred, 0.05 mol or more is more preferred, and 0.1 mol or more is particularly preferred.
• the amount of the Lewis acid used is preferably 10 mol or less, more preferably 5 mol or less, and particularly preferably 1 mol or less, per 1 mol of the organic alkali metal compound. If the amount of the Lewis acid used relative to 1 mol of the organic alkali metal compound is less than 0.01 mol, the effect of the addition of the Lewis acid is poor and it is difficult to adjust the desired degree of vinylation. The rate of chain polymerization tends to decrease, and the economy tends to be poor.
• the amount of the Lewis acid used is preferably 0.02 mol or more, more preferably 0.1 mol or more, and 0.2 mol or more, relative to 1 mol of the polar compound used in the step (A-1). Especially preferred.
• the amount of the Lewis acid to be used is preferably 20 mol or less, more preferably 10 mol or less, and particularly preferably 2 mol or less, relative to 1 mol of the polar compound. If the amount of the Lewis acid used relative to 1 mol of the polar compound is less than 0.02 mol, the effect of adding the Lewis acid is poor and it is difficult to adjust the degree of vinylation to the desired degree. The polymerization rate tends to decrease, and the economy tends to be poor.
• the timing of adding the Lewis acid may be after step (A-1), before step (B) described later, or at any timing during step (B). Well, it can be arbitrarily selected depending on the vinyl content of the desired side chain (b).
• Step (B) A method for producing a conjugated diene-based graft polymer by the MI method, (B) adding at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound to polymerize from the remaining lithiated anionic active sites in the polymer (M) to obtain a main chain A step of forming a side chain on the polymer (M) to produce a conjugated diene-based graft polymer; including.
• the monomer polymerized in the step (B) becomes the side chain (b) of the conjugated diene-based graft polymer of the present invention.
• conjugated diene which is a monomer unit constituting the polymer polymerized in the step (B), preferred content thereof, and other monomers other than the conjugated diene (aromatic vinyl compound etc.) are the same as those for the side chain (b) of the conjugated diene graft polymer.
• the description of the weight average molecular weight (Mn), vinyl content, suitable aspects of Tg, etc. of the polymer polymerized in the step (B) is the same as the description of the side chain (b) of the conjugated diene-based graft polymer. .
• a polar compound may be further added in order to adjust the vinyl content of the side chain (b) to the desired range.
• a Lewis acid may also be added as described above to adjust the vinyl content to the desired range.
• Solvents that can be used in the step (B) are the same as the preferred examples of the solvent in the step (A-1). If necessary, a solvent may be further added at any timing after step (A-1).
• the polymerization temperature in the step (B) is preferably 0°C or higher, more preferably 10°C or higher, and particularly preferably 20°C or higher.
• the polymerization temperature is preferably 100° C. or lower, more preferably 80° C. or lower, and particularly preferably 60° C. or lower. If the polymerization temperature is less than 0°C, the polymerization rate tends to be poor, and if it exceeds 100°C, side reactions such as decomposition tend to increase.
• the polymerization time in the step (B) can be appropriately set according to the progress of the reaction, but is preferably 0.01 to 100 hours, more preferably 0.1 to 50 hours, and particularly preferably 0.2 to 20 hours. .
• the polymerization reaction in the above step (B) can be terminated by adding a polymerization terminator.
• a polymerization terminator examples include alcohols such as methanol and isopropanol.
• the conjugated diene-based graft polymer obtained by the production method including the steps (A-1), (B), and (D) without including the step (C) described in detail below is not hydrogenated. It is a conjugated diene-based graft polymer.
• Step (C) In the method for producing a conjugated diene-based graft polymer by the MI method, before the step (D), (C) hydrogenating at least part of the carbon-carbon double bonds contained in the conjugated diene units in the conjugated diene-based graft polymer; It is a preferred embodiment to include
• a hydrogenated conjugated diene-based graft polymer can be obtained by subjecting the conjugated diene-based graft polymer obtained by the above method to a step of hydrogenating.
• the hydrogenation method is not particularly limited, and for example, a known method can be used.
• the above step (B) and hydrogenation may be carried out successively, or the non-hydrogenated conjugated diene-based graft polymer may be isolated once and then hydrogenated.
• the method for isolating the non-hydrogenated conjugated diene-based graft polymer is the same as the recovery step (D) described below.
• a catalyst that can hydrogenate carbon-carbon double bonds contained in olefin compounds and the like can be used.
• Such catalysts generally include heterogeneous catalysts, homogeneous catalysts, and the like.
• the heterogeneous catalyst is not particularly limited, but specific examples include sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper; nickel silica, nickel alumina, nickel zeolite, nickel diatomaceous earth, palladium silica, palladium alumina, palladium Zeolite, palladium diatomaceous earth, palladium carbon, palladium calcium carbonate, platinum silica, platinum alumina, platinum zeolite, platinum diatomaceous earth, platinum carbon, platinum calcium carbonate, ruthenium silica, ruthenium alumina, ruthenium zeolite, ruthenium diatomaceous earth, ruthenium carbon, ruthenium calcium carbonate, supported metal catalysts such as iridium silica, iridium alumina, iridium zeolite, iridium diatomaceous earth, iridium carbon, iridium calcium carbonate, cobalt silica, cobalt alumina, cobalt zeolite
• the homogeneous catalyst is not particularly limited, but specific examples thereof include Ziegler catalysts composed of a transition metal compound and alkylaluminum or alkyllithium; metallocene catalysts.
• transition metal compounds used in Ziegler-based catalysts include nickel salts such as nickel acetate, nickel octylate and nickel acetylacetonate; cobalt salts such as cobalt acetate, cobalt octylate and cobalt acetylacetonate; titanocene dichloride and zirconocene. dichlorides.
• alkylaluminums used in Ziegler catalysts include trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum.
• alkyllithium used in Ziegler catalysts include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and t-butyllithium. These homogeneous catalysts may be used singly or in combination of two or more. Moreover, the homogeneous catalyst may be used in combination with the heterogeneous catalyst.
• step (C) since the polymer is hydrogenated, the reaction activity for low-molecular-weight compounds is generally low. Therefore, in many cases, relatively high temperature and high pressure conditions are preferable as the reaction conditions, and it is preferable to use a heterogeneous catalyst with high thermal stability. From the aspect of hydrogenation activity, it is preferable to use nickel or palladium as the metal having hydrogenation activity. Moreover, in order to suppress undesirable side reactions during the hydrogenation reaction, it is preferable to use calcium carbonate or a carbon support as the support, and it is more preferable to use a carbon support.
• the hydrogenation reaction is usually carried out in an organic solvent.
• an organic solvent is not particularly limited, and for example, the solvents exemplified in the above step (B) or step (E) described later can be used.
• the above hydrogenation reaction is carried out, for example, in a state in which the unhydrogenated conjugated diene-based graft polymer is present in the solvent used in the above step (B), without subjecting the organic solvent to any particular treatment.
• the reaction may be carried out in the remaining solvent, or after dilution with an organic solvent, the reaction may be carried out in the solvent.
• the conjugated diene-based graft polymer that is not hydrogenated is once taken out, and this conjugated diene-based graft polymer is put into an organic solvent, and a hydrogenation reaction is performed in the solvent. good too.
• the amount of the organic solvent used is such that the concentration of the unhydrogenated conjugated diene-based graft polymer in the reaction solution is 1% by mass or more and 30% by mass or less. Preferably. If the concentration is less than 1% by mass, the productivity may be significantly reduced, and if it exceeds 30% by mass, the viscosity may be significantly increased and the mixing efficiency may be reduced.
• the reaction pressure of the hydrogenation reaction may be appropriately set according to the catalyst used, etc., but the total pressure is usually 0.1 MPa to 20 MPa, preferably 0.5 MPa to 15 MPa, more preferably 0.5 MPa to 5 MPa. be.
• the hydrogenation reaction is carried out in the presence of hydrogen gas, but it may be carried out in the presence of a gas mixed with a gas other than hydrogen gas that is inert to the hydrogenation reaction.
• gases inert to the hydrogenation reaction include nitrogen, helium, argon, and carbon dioxide.
• the solvent used in the reaction may have a significant partial pressure as a gas component, but such a situation is usually not a problem as long as the hydrogenation reaction proceeds.
• the reaction temperature for the hydrogenation reaction may be appropriately set according to the catalyst used, but is usually 20°C to 250°C, preferably 50°C to 180°C, more preferably 70°C to 180°C. In general, it may be desirable for heterogeneous catalysts to react at higher temperatures than homogeneous catalysts.
• the reaction time for the hydrogenation reaction may be appropriately set according to the type of catalyst used, the amount of catalyst and the reaction temperature, and is usually 0.1 to 100 hours, preferably 1 to 50 hours. If the reaction time is too short, the desired hydrogenation rate may not be obtained. On the other hand, if the reaction time is too long, undesired side reactions may proceed remarkably, and a hydrogenated conjugated diene-based graft polymer having desired physical properties may not be obtained.
• the reaction form of the hydrogenation reaction is not particularly limited, and may be appropriately set according to the type of catalyst used in the reaction.
• the reaction format include a batch reaction format, a semi-continuous reaction format (semi-batch reaction format), and a continuous reaction format.
• Suitable continuous reaction formats include plug flow format (PFR), continuous flow stirred format (CSTR), and the like.
• PFR plug flow format
• CSTR continuous flow stirred format
• the hydrogenation reaction can be carried out using a fixed bed reactor.
• the mixing method includes a mixing method by stirring and a mixing method in which the reaction solution is circulated in a loop.
• the reaction When a heterogeneous catalyst is used under mixed conditions, the reaction is by a suspended bed and becomes a gas-liquid-solid reaction field. Further, when a homogeneous catalyst is used under mixed conditions, the reaction field becomes a gas-liquid two-phase system. Hydrogen in a reaction format in which the hydrogenation reaction in the reaction vessel is once terminated, the reaction liquid is withdrawn, and at least part of the withdrawn reaction liquid is charged into the same or different reaction vessel to further perform the hydrogenation reaction. An addition reaction may be performed. By carrying out the hydrogenation reaction in such a reaction format, if it is possible to avoid localization of the heat generation accompanying the hydrogenation reaction, the hydrogenation rate may be improved.
• the hydrogenation reaction may be carried out in a single reaction format, or in combination of two or more reaction formats that are the same or different.
• it may be desirable to use a fixed-bed reactor and use a hydrogenation reaction step that includes a plug-flow reaction step.
• the amount of catalyst used in the hydrogenation reaction may be appropriately set according to the type of catalyst used, the concentration of the non-hydrogenated conjugated diene graft polymer, and the reaction mode.
• the amount of the catalyst used per 100 parts by mass of the reaction liquid containing the unhydrogenated conjugated diene graft polymer is usually 0.01 to 20 parts by mass, preferably 0.05 to 20 parts by mass. 15 parts by mass, more preferably 0.1 to 10 parts by mass. If the amount of catalyst used is too small, the hydrogenation reaction may require a long time, and if the amount of catalyst used is too large, more power may be required to mix the heterogeneous catalyst.
• the amount of catalyst to be used per reaction liquid containing unhydrogenated conjugated diene-based graft polymer can be set as appropriate.
• Ziegler catalyst as a homogeneous catalyst; when a metallocene catalyst is used, the concentration in the reaction solution containing the unhydrogenated conjugated diene graft polymer of the transition metal compound is usually 0.001 mmol/liter to 100 mmol. /liter, preferably 0.01 mmol/liter to 10 mmol/liter.
• the catalyst used for the hydrogenation reaction may be separated from the liquid containing the hydrogenated conjugated diene-based graft polymer, if necessary, after the completion of the hydrogenation reaction.
• the separation method is not particularly limited as long as the catalyst can be separated. If a heterogeneous catalyst is used, the catalyst can be separated by, for example, continuous or batch filtration, centrifugation, settling by settling and decantation. When a homogeneous catalyst is used, the catalyst can be separated by, for example, coagulation sedimentation, adsorption, washing and aqueous phase extraction. Even if the used catalyst is separated by these separation methods, trace amounts of metal components derived from the catalyst may remain in the liquid containing the hydrogenated conjugated diene-based graft polymer.
• the remaining metal component can be separated by a separation method such as coagulation sedimentation, adsorption, washing, and aqueous phase extraction, as described above.
• the catalyst recovered by separation can be used again for the hydrogenation reaction after removing part of it or adding a new catalyst, if necessary.
• Step (D) A method for producing a conjugated diene-based graft polymer by the MI method, (D) a step of recovering the obtained conjugated diene-based graft polymer; including.
• step (D) the obtained conjugated diene-based graft polymer of the present invention is recovered.
• the method for recovering the conjugated diene-based graft polymer is not particularly limited. is poured into a poor solvent such as methanol to precipitate a conjugated diene-based graft polymer, or the polymerization reaction solution is poured into hot water with steam to remove the solvent by azeotropic distillation (steam stripping). After that, the conjugated diene-based graft polymer can be recovered by isolating it by drying, or by washing the polymerization reaction solution with water, separating it, and drying it.
• step (D) may be carried out by the method described above.
• An antioxidant may be added to the conjugated diene-based graft polymer of the present invention in any of the steps described above, if necessary. For example, it may be added after step (B), after step (C) or at each step during step (D), or after step (D) or at each step during step (D).
• Preferred anti-aging agents used at this time include, for example, 2,6-di-t-butyl-4-methylphenol (BHT), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4 '-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol) (AO-40), 3,9-bis[1,1-dimethyl- 2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80), 2,4-bis[(octylthio)methyl]-6-methylphenol (Irganox 1520L), 2,4-bis[(dodecylthio)methyl]-6-methylphenol (Irganox 1726), 2-[1-(2-hydroxy- 3,5-di-t-pentylphen
• CP method ⁇ Coupling method (CP method)>
• CP method a production method by a coupling method (CP method) including the following steps (E) and (D) is a preferred embodiment.
• P represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and X represents an anionic polymerization active terminal.
• X represents an anionic polymerization active terminal.
• the active terminal polymer (I) used in the above step (E) can be produced using a known polymerization method. For example, in a solvent inert to the polymerization terminal, using an anionically polymerizable active metal or active metal compound as an initiator, optionally in the presence of a polar compound, by anionically polymerizing a monomer, the active terminal is polymerized. Coalescence (I) can be obtained. The P of this active terminal polymer (I) becomes the side chain (b) of the conjugated diene-based graft polymer obtained in the present invention.
• an organic alkali metal compound is preferred, and an organic lithium compound is more preferred.
• the organic lithium compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.
• the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; and benzene. , toluene, and xylene; and ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether.
• aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane
• alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane
• benzene toluene, and xylene
• ether compounds
• a polar compound may be added during the anionic polymerization.
• Polar compounds are commonly used in anionic polymerizations to control the microstructure (vinyl content) of the conjugated diene units without quenching the reaction.
• Examples of polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
• the polar compound is generally used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
• the temperature of the anionic polymerization is usually in the range of -80 to 150°C, preferably in the range of 0 to 100°C, more preferably in the range of 10 to 90°C.
• the mode of polymerization may be either a batchwise system or a continuous system.
• the P of the above active terminal polymer (I) finally becomes the side chain (b) of the conjugated diene-based graft polymer of the present invention.
• the descriptions of the number average molecular weight (Mn) of P, the vinyl content, the preferred aspects of Tg, etc. of the active terminal polymer (I) are the same as those relating to the side chain (b) of the conjugated diene graft polymer of the present invention. be.
• the functional group-modified conjugated diene-based polymer (F) is obtained, for example, by modifying the unmodified conjugated diene-based polymer (F') with a functional group in the modification step described below.
• the method for producing the unmodified conjugated diene-based polymer (F′) is not particularly limited, and can be applied in the same manner as the method for producing the polymer (M) containing conjugated diene units described above.
• the portion other than the functional group-modified conjugated diene polymer (F) becomes the main chain (a) of the conjugated diene graft polymer of the present invention.
• conjugated diene which is a monomer unit constituting the unmodified conjugated diene-based polymer (F'), preferred content thereof, and other monomers other than the conjugated diene (aromatic vinyl compound, etc.) are the same as those for the main chain (a) of the conjugated diene-based graft polymer.
• the number average molecular weight (Mn), vinyl content, preferred aspects of Tg, etc. of the unmodified conjugated diene-based polymer (F') are the same as those for the main chain (a) of the conjugated diene-based graft polymer. be.
• the method for producing the functional group-modified conjugated diene polymer (F) having an epoxy group by modifying the unmodified conjugated diene polymer (F') with a functional group is not particularly limited, and conventionally known methods can be used. It can be according to the method. For example, by epoxidizing the unmodified conjugated diene-based polymer (F′) using an epoxidizing agent such as hydroperoxides and organic peracids, a functional group-modified conjugated diene-based polymer (F ) can be manufactured. Hydroperoxides include hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like.
• organic peracids include performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, m-chloroperbenzoic acid and the like.
• the organic peracid may be an equilibrium peracid using hydrogen peroxide and an organic acid.
• a catalyst may be used in the epoxidation reaction.
• Combinations of the epoxidizing agent and the catalyst include, for example, when the epoxidizing agent is a hydroperoxide, a combination of hydrogen peroxide and a mixture of tungstic acid and caustic soda, a combination of hydrogen peroxide and an organic acid, t- Examples include a combination of butyl hydroperoxide and molybdenum hexacarbonyl.
• the epoxidizing agent is an organic peracid, a combination of an organic peracid and an alkali such as sodium carbonate or an acid such as sulfuric acid may be used.
• phase-transfer heteropolyacids prepared from heteropolyacids containing tungsten or molybdenum (especially 12-tungstophosphoric acid) and surfactants (especially halogenated quaternary ammonium salts).
• a method of epoxidation with hydrogen peroxide in a two-phase system of an aqueous phase and an organic phase in the presence of an acid is also included.
• the amount of the epoxidizing agent and the catalyst used is not particularly limited, and can be appropriately set according to the type of polymer to be epoxidized, the type of epoxidizing agent, the degree of epoxidation of the polymer to be epoxidized, and the like. .
• the epoxidation reaction can be carried out in the absence of a solvent, but it may also be carried out in the presence of a solvent that is inert to the epoxidizing agent.
• Solvents that can be used for the epoxidation reaction include aliphatic hydrocarbons such as hexane and heptane, esters such as ethyl acetate, aromatic hydrocarbons such as benzene and xylene, and halogenated hydrocarbons such as chloroform and carbon tetrachloride. Hydrogen is mentioned.
• the reaction temperature of the above epoxidation reaction is usually in the range of 0 to 140°C, preferably 0 to 80°C, more preferably 10 to 40°C, from the viewpoints of reaction rate, reaction selectivity, safety, and the like. If the reaction temperature is too low, the reaction rate tends to decrease. From the viewpoint of safety, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.
• the reaction time can be appropriately set according to the desired epoxidation rate, and is, for example, 1 to 48 hours, preferably 4 to 36 hours, more preferably 8 to 36 hours.
• the average number of epoxy groups per molecule of the functional group-modified conjugated diene polymer (F) is preferably 2 to 150, more preferably 3 to 90, and even more preferably 4 to 70.
• the average number of epoxy groups per molecule of the functional group-modified conjugated diene polymer (F) is determined by the epoxy equivalent (g/eq) contained in the functional group-modified conjugated diene polymer (F) and the functional group-modified conjugated diene system. It is obtained from the following formula (4) using the number average molecular weight (Mn) of the polymer (F) in terms of standard polystyrene.
• the epoxy equivalent of the epoxy group contained in the functional group-modified conjugated diene-based polymer (F) is the conjugated diene bonded per epoxy group and other monomers other than the conjugated diene optionally contained. means body mass.
• the epoxy equivalent is calculated from the area ratio of the peak derived from the epoxy group and the peak derived from the main chain of the polymer using 1 H-NMR.
• the description of the number average molecular weight (Mn), vinyl content, preferred aspects of Tg, etc. of the functional group-modified conjugated diene-based polymer (F) is the same as that of the unmodified conjugated diene-based polymer (F').
• the melt viscosity of the functional group-modified conjugated diene polymer (F) measured at 38° C. is preferably 0.01 to 2,000 Pa s, more preferably 0.05 to 1500 Pa s, and 0.1 to 1000 Pa. • s is more preferred.
• the melt viscosity of the functional group-modified conjugated diene-based polymer (F) is within the above range, it tends to be excellent in the ability to pass the process during production and to be economically efficient.
• step (E) by reacting the active terminal polymer (I) with the functional group-modified conjugated diene polymer (F), the epoxy groups in the functional group-modified conjugated diene polymer (F) and the active
• the terminal polymer (I) reacts to form a conjugated diene-based graft polymer in which the active terminal polymer (I) as a side chain is bound to the main chain (a) (hereinafter, this reaction is referred to as a coupling reaction (referred to as An example of the coupling reaction when epoxy-modified polybutadiene is used as the functional group-modified conjugated diene polymer (F) is shown in the following formula (II).
• P represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units.
• the epoxy groups in the functional group-modified conjugated diene-based polymer (F) are ring-opened so that the main chain (a) of the conjugated diene-based graft polymer A hydroxyl group is formed that bonds to
• the hydroxyl group is directly bonded to atoms (typically carbon atoms) constituting the main chain (a) other than the atoms bonded to the side chain (b).
• the average number of epoxy groups per molecule of the functional group-modified conjugated diene polymer (F) can be appropriately set according to the average number of hydroxyl groups bonded to the main chain (a) described above.
• the average number of epoxy groups per molecule of the functional group-modified conjugated diene polymer (F) is 4, hydroxyl groups bonded to the main chain (a) per molecule of the finally obtained conjugated diene graft polymer can be designed to have an average number of four.
• the average number may be appropriately set to a desired value. If the molar ratio of (charged amount of active terminal polymer (I))/(charged amount of functional group-modified conjugated diene-based polymer (F)) is less than 2, the number of side chains that can be introduced is less than 200. If it is too large, the coupling rate, which will be described later, tends to decrease.
• the above coupling reaction is usually carried out at a temperature of 0 to 100° C. for 0.5 to 50 hours.
• the functional group-modified conjugated diene-based polymer (F) may be diluted before use, and the solvent for dilution is not particularly limited as long as it is inert to the active terminal and does not adversely affect the reaction. Examples include hexane and cyclohexane. , heptane, octane, decane, toluene, benzene, xylene and other saturated aliphatic or aromatic hydrocarbons. Also, a Lewis base may be added as an additive during the coupling reaction.
• Lewis bases include, for example, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N,N,N',N'-tetramethylethylenediamine, N-methylmorpholine; amines such as These Lewis bases may be used singly or in combination of two or more.
• the functional group-modified conjugated diene polymer (F) may be added to the reaction system in which the active terminal polymer (I) was synthesized, or conversely, the functional group-modified conjugated diene
• the active terminal polymer (I) may be added to the system containing the system polymer (F).
• both the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) may be used after being diluted with a solvent, if necessary.
• the active terminal polymer (I) may be used alone or in combination of two or more.
• the functional group-modified conjugated diene polymer (F) may also be used alone. may be used in combination of two or more.
• the coupling rate in the above coupling reaction is preferably 40% or higher, more preferably 50% or higher, even more preferably 60% or higher. If the coupling ratio is less than 40%, the resulting conjugated diene-based graft polymer will have poor mechanical properties, which is not preferable.
• the coupling rate can be adjusted by increasing the amount of the functional group-modified conjugated diene polymer (F) added to the active terminal polymer (I), by increasing the amount of the Lewis base added to the active terminal polymer (I), It can be increased by raising the reaction temperature or lengthening the reaction time.
• the coupling reaction can be carried out until the coupling rate reaches the desired range. After that, the coupling reaction can be stopped by adding a polymerization terminator such as methanol or isopropanol.
• the conjugated diene-based graft polymer obtained by the production method including the step (E) and the step (D) without including the step (C) described in detail below is a non-hydrogenated conjugated diene-based graft polymer. be.
• Step (C) In the method for producing a conjugated diene-based graft polymer of the present invention, before step (D), (C) hydrogenating at least part of the carbon-carbon double bonds contained in the conjugated diene units in the conjugated diene-based graft polymer; It is a preferred embodiment to include
• a hydrogenated conjugated diene graft polymer can be obtained by subjecting the non-hydrogenated conjugated diene graft polymer obtained by the above method to a step of hydrogenating.
• the method for hydrogenating the conjugated diene-based graft polymer is not particularly limited, and the same method as the method for hydrogenating the conjugated diene-based graft polymer described as the step (C) of the MI method described above can be applied.
• the method for producing a conjugated diene-based graft polymer of the present invention comprises: (D) a step of recovering the obtained conjugated diene-based graft polymer; including.
• step (D) the obtained conjugated diene-based graft polymer used in the present invention is recovered.
• the recovery method of the conjugated diene-based graft polymer is not particularly limited, and the same method as the recovery method of the conjugated diene-based graft polymer described as the step (D) of the MI method described above can be applied.
• An antioxidant may be added to the conjugated diene-based graft polymer of the present invention in any of the steps described above, if necessary. For example, it may be added after step (E), after step (C) or at each step during step (D), or after step (D) or at each step during step (D).
• Preferred anti-aging agents used at this time are the same anti-aging agents exemplified in the step of the MI method described above.
• the conjugated diene-based graft polymer of the present invention can be suitably used as a lubricating oil additive.
• a lubricating oil additive preferred embodiments are the same as those for the conjugated diene-based graft polymer.
• examples of lubricating oil additives include viscosity index improvers and friction inhibitors, which will be described later.
• the conjugated diene-based graft polymer of the present invention can be suitably used as a viscosity index improver.
• preferred embodiments are the same as the preferred embodiments of the conjugated diene-based graft polymer.
• the conjugated diene-based graft polymer of the present invention can be suitably used as a friction inhibitor.
• preferred embodiments are the same as the preferred embodiments of the conjugated diene-based graft polymer.
• the oil composition of the present invention comprises a base oil and a lubricating oil additive (preferably a viscosity index improver or friction inhibitor) comprising the conjugated diene-based graft polymer of the present invention.
• a lubricating oil additive preferably a viscosity index improver or friction inhibitor
• the base oil is not particularly limited, and for example, known base oils can be used.
• Base oils include, for example, fuel oils such as middle distillate fuels, synthetic and natural lubricating oils, unrefined oils and industrial oils.
• the base oil may be at least one of paraffinic base oil, naphthenic base oil and aromatic base oil, or at least one of natural oil and synthetically prepared oil.
• the base oil may be any base oil of Groups I to V in the classification of API (American Petroleum Institute), but from the viewpoint of economy, base oils of Groups I to III are preferred. preferable.
• Base oils that can be used in the oil composition of the present invention include, for example, base oils described in Japanese Patent No. 5933263 and JP-A-2005-23320.
• the oil composition of the present invention contains a lubricating oil additive (viscosity index improver, friction inhibitor) comprising the conjugated diene graft polymer of the present invention.
• the content of the lubricating oil additive (viscosity index improver, friction inhibitor) in the oil composition can be appropriately adjusted so that the viscosity, viscosity index or frictional properties of the lubricating oil are within the desired range. It is preferably 1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 0.5 to 10% by mass.
• the content of the lubricating oil additive (viscosity index improver, friction inhibitor) is within the above range, the lubricating oil tends to have an excellent balance between performance and economy.
• the oil composition of the present invention contains additives such as rust inhibitors, antioxidants, surfactants, pour point depressants, detergent dispersants, metal deactivators, defoamers, friction modifiers and extreme pressure agents. may contain These additives may be used singly or in combination of two or more.
• the method for producing the oil composition of the present invention is not particularly limited as long as the oil composition can be produced, for example, mixing the base oil and the lubricating oil additive (viscosity index improver, friction inhibitor).
• can be manufactured by Mixing can be performed, for example, using a known mixing device. Mixing is preferably carried out while heating. The heating temperature is preferably 80-180°C.
• kinematic viscosity at 40° C. is preferably in the range of 20 to 300 mm 2 /sec, preferably 25 to 300 mm 2 /sec. A range of 150 mm 2 /sec is preferred. From the same point of view, the kinematic viscosity at 100° C. is preferably in the range of 3 to 30 mm 2 /sec, more preferably in the range of 4 to 20 mm 2 /sec. Within this range, the fuel consumption of the vehicle can be reduced when used for the above applications. In the present invention, kinematic viscosity is a value measured according to JIS K2283:2000.
• the shear stability is preferably in the range of 0 to 20%, more preferably in the range of 0 to 10%. is more preferred, and a range of 0 to 4% is particularly preferred.
• the degree of shear stability is determined according to JPI-5S-29-2006 using an oil composition adjusted to have a kinematic viscosity at 100° C. of 6.9 to 9.3 mm 2 /sec. It is a value obtained by measuring the rate of decrease in kinematic viscosity at 100°C.
• the conjugated diene-based graft polymer obtained in the present invention can be used as an oil composition by mixing with the base oil.
• An oil composition containing this conjugated diene-based graft polymer and a base oil can be used, for example, in a cosmetic composition constituting a cosmetic product.
• Cosmetic products include, for example, hair make-up products such as shampoos, hair setting gels or lotions, blow-drying lotions, fixing and styling agents; Lip makeup products such as lipsticks, liquid lipsticks, and lip glosses; Cleansing products such as facial cleansing foams and makeup removers; mentioned.
• oil composition can be used as asphalt modifiers, adhesives, adhesives, resin modifiers, compatibilizers, sealants, coating materials, molded products, fibers and nonwoven fabrics, drilling fluids, optical fiber cables and electric cables. It can be used as an internal buffer for cables such as
• Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn) By gel permeation chromatography (GPC), the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) of the conjugated diene-based graft polymer and the polymer at each stage of its production were measured. Calculated in terms of standard polystyrene.
• Eluent Tetrahydrofuran Eluent flow rate: 0.35 mL/min
• Vinyl content, styrene unit (structural unit derived from styrene) content, hydrogenation rate 1 H-NMR, conjugated diene graft polymer, vinyl content of polymer at each stage of its production, and styrene A unit content and a hydrogenation rate were calculated.
• the vinyl content was calculated from the area ratio of the peak of the double bond derived from the vinylated conjugated diene unit in the obtained spectrum and the peak of the double bond derived from the non-vinylated conjugated diene unit.
• the styrene unit content was calculated from the area ratio of the peak of the derived aromatic ring and the peak of the double bond derived from the conjugated diene unit.
• the vinyl content and styrene unit content were obtained by using 1 H-NMR of the conjugated diene graft polymer before hydrogenation.
• the hydrogenation rate was calculated from the peak ratio of the double bond derived from the conjugated diene unit of the conjugated diene graft polymer before hydrogenation and the conjugated diene graft polymer after hydrogenation.
• Apparatus Nuclear magnetic resonance apparatus "JNM-ECX400" manufactured by JEOL Ltd.
• Solvent Heavy chloroform Measurement temperature: 50°C Accumulated times: 1024 times
• Average number of side chains (b) per molecule of conjugated diene-based graft polymer is In the case of production by a method of polymerizing a monomer that becomes a structural unit of a side chain after the main chain is lithiated by reacting the coalescence with an organic alkali metal compound in the presence of tetramethylethylenediamine, the lithiation reaction is carried out. It was calculated from the charge ratio of the organic alkali metal used, the conjugated diene polymer as the structural unit of the main chain, and the functionalizing agent added as necessary.
• the active terminal of the polymer obtained by polymerizing the epoxy group contained in the monomer unit that will be the branch portion of the functional group-modified polymer that will be the main chain (a) described later and the monomer that will be the structural unit of the side chain In the case of production by a method of reacting with , it was calculated from the charging ratio of the active terminal polymer and the functional group-modified conjugated diene polymer, which are the constituents of the side chain (b) in the coupling reaction.
• the side chain density of the side chain (b) is the average number of side chains (b) per molecule of the conjugated diene graft polymer and the standard polystyrene of the main chain (a). It was calculated from the following formula (1) using the converted number average molecular weight (Mn).
• Side chain density (average number of side chains (b) per molecule of conjugated diene graft polymer)/[(number average molecular weight Mn of main chain (a))/(molecular weight of styrene unit)] x 100 (1)
• Average number of hydroxyl groups bonded to main chain (a) per molecule of conjugated diene graft polymer The average number of hydroxyl groups bonded to the main chain (a) per molecule of the conjugated diene graft polymer is As follows, using the hydroxyl value (mgKOH / g) of the conjugated diene graft polymer calculated in accordance with JIS K1557-1: 2007 and the number average molecular weight (Mn) converted to standard polystyrene of the conjugated diene graft polymer Obtained from the formula (2).
• Concentration of hydroxyl groups The concentration of hydroxyl groups bonded to the main chain (a) is the average number of hydroxyl groups bonded to the main chain (a) per molecule of the conjugated diene graft polymer and the standard polystyrene conversion of the main chain (a). It calculates
• requires from following formula (3) using a number average molecular weight (Mn). (Hydroxy group concentration) (average number of hydroxyl groups bonded to main chain (a) per molecule of conjugated diene graft polymer)/[(number average molecular weight Mn of main chain (a))/(molecular weight of styrene unit) ] ⁇ 100 (3)
• Viscosity index A base oil/conjugated diene graft prepared by using SK Lubricants Group III base oil "YUBASE4" as the base oil and adjusting the kinematic viscosity at 100°C to 6.9 to 9.3 mm 2 /sec. The viscosity index was measured according to JIS K2283:2000 using the oil composition comprising the polymer.
• Friction coefficient (relative value)
• SK Lubricants Group III base oil "YUBASE4" as the base oil
• an oil composition composed of the base oil/conjugated diene graft polymer was prepared so that the kinematic viscosity at 100°C was 6.0 mm 2 /sec.
• the absolute value of the coefficient of friction of the obtained oil composition was measured using an MTM mini-traction tester manufactured by PCS Instruments under the following conditions.
• the coefficient of friction of the object was similarly measured.
• the friction-reducing effect of the conjugated diene-based graft polymer was evaluated based on the relative value when the friction coefficient of the reference oil was taken as 100.
• ⁇ Measurement conditions> ⁇ Temperature: 100°C ⁇ Load: 40N ⁇ Peripheral speed: 50mm/s ⁇ Slip rate: 50% ⁇ Material: steel ball, steel disc
• Example 1 (Step (1)) A sufficiently dried 5 L autoclave was purged with nitrogen, charged with 1430 g of cyclohexane, 223 g of sec-butyllithium (10.5% by mass cyclohexane solution) and 15 g of tetrahydrofuran, heated to 50° C., and the polymerization temperature was raised to 50 under stirring conditions. 1,350 g of butadiene was added successively while controlling the temperature to be 0° C., and polymerization was carried out for 1 hour. After that, 13 g of methanol was added to terminate the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water. After finishing the stirring and confirming that the polymer solution phase and the water phase were separated, the water was separated. The unmodified conjugated diene polymer (F'-1) was obtained by vacuum-drying the polymer solution after washing at 70° C. for 24 hours.
• Step (2) Subsequently, 200 g of the unmodified conjugated diene polymer (F'-1) obtained in step (1), 3800 g of chloroform, 12-tungstophosphate hydrate (H 3 PW 12 60 g of O 40 .30H 2 O), 60 g of hexadecylpyridinium chloride and 51 g of 35% by weight hydrogen peroxide were charged and stirred at room temperature for 15 hours under nitrogen atmosphere. After the reaction, water was added and stirred, the aqueous phase was removed, and the mixture was washed with a 10% by weight aqueous solution of sodium hydrogen sulfite.
• the resulting functional group-modified conjugated diene polymer (F-1) had a number average molecular weight of 7,000, a vinyl content of 50 mol%, and an epoxy per molecule of the functional group-modified conjugated diene polymer (F-1). The average number of groups was three. 720 g of toluene was added to 180 g of the obtained functional group-modified conjugated diene polymer (F-1) to dilute it to a concentration of 20% by mass, and the functional group-modified conjugated diene polymer (F-1) used in the coupling reaction described later was obtained. A diluted solution of 1) was obtained.
• Step (3) A sufficiently dried 5 L autoclave is purged with nitrogen, charged with 1670 g of toluene and 80 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then brought to a polymerization temperature of 50°C under stirring conditions. While controlling as above, 440 g of isoprene was successively added and polymerized for 1 hour to obtain an active terminal polymer (I-1). By sampling and analyzing the polymer solution in step (3), the number average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-1) described later are determined. be able to. The obtained active terminal polymer (I-1) had a number average molecular weight of 5,000, a vinyl content of 10 mol % and a styrene unit content of 0 mass %.
• Step (4) Subsequently, 810 g of a diluted solution of the functional group-modified conjugated diene polymer (F-1) obtained in step (2) is added to the solution containing the active terminal polymer (I-1) obtained in step (3). and the coupling reaction was carried out at 50° C. for 2 hours. After that, 8.7 g of methanol was added to terminate the reaction to obtain a polymer solution.
• Step (5) 450 mL of a Ziegler hydrogenation catalyst (0.095 mmol/L cyclohexane solution) formed from nickel octylate and trimethylaluminum was added to the resulting polymer solution, and the reaction was allowed to proceed for 10 hours under conditions of a hydrogen pressure of 1 MPa and 80°C. to obtain a solution containing the conjugated diene-based graft polymer (G-1).
• a Ziegler hydrogenation catalyst 0.095 mmol/L cyclohexane solution formed from nickel octylate and trimethylaluminum
• Step (6) Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water. After finishing the stirring and confirming that the polymer solution phase and the water phase were separated, the water was separated.
• the conjugated diene-based graft polymer (G-1) was recovered by vacuum-drying the polymer solution after washing at 70° C. for 24 hours.
• the obtained conjugated diene-based graft polymer (G-1) had a weight average molecular weight of 22,000, an Mw/Mn of 1.5, a structural unit content derived from styrene of 0% by mass, and a hydrogenation rate of 85 mol.
• the average number of hydroxyl groups bonded to the main chain per polymer molecule is 3, the hydroxyl group concentration is 4.5 mol%, the average number of side chains (b) per polymer molecule is 3, the side chain The density was 4.5 mol%.
• the atom bonded to the side chain (b) contained in the monomer unit that becomes the branched portion is not a hetero atom, and the linking portion containing the atom bonded to the side chain (b) is an aromatic vinyl compound-derived aromatic not a tribe.
• Table 3 shows the molecular specifications and physical properties of the resulting conjugated diene-based graft polymer (G-1).
• Example 2 A conjugated diene-based graft polymer (G-2 ) to (G-4) were obtained.
• Table 3 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymers (G-2) to (G-4).
• Step (1) A sufficiently dried 5 L autoclave is purged with nitrogen, charged with 1470 g of cyclohexane and 177 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then brought to a polymerization temperature of 50°C under stirring conditions. While controlling as above, 1350 g of isoprene was added successively and polymerized for 1 hour. After that, 10 g of methanol was added to terminate the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water.
• conjugated diene polymer (M-1) After finishing the stirring and confirming that the polymer solution phase and the water phase were separated, the water was separated. After washing, the polymer solution was vacuum-dried at 70° C. for 24 hours to obtain a conjugated diene polymer (M-1). Analysis of the obtained conjugated diene-based polymer (M-1) can determine the number average molecular weight and vinyl content of the main chain (a) of the conjugated diene-based graft polymer (G-5) described later. The resulting conjugated diene polymer (M-1) had a number average molecular weight of 7,000 and a vinyl content of 10 mol %.
• Step (2) Subsequently, 111 g of the conjugated diene polymer (M-1) obtained in step (1) was charged into a sufficiently dried 5 L autoclave, and the polymer was degassed with nitrogen while stirring at 60° C. for 3 hours. And the inside of the autoclave was replaced with nitrogen. After charging 1230 g of cyclohexane and raising the temperature to 40° C., 87 g of sec-butyllithium (10.5% by mass cyclohexane solution) and 9.2 g of N,N,N',N'-tetramethylethylenediamine were sequentially added, The lithiation reaction was carried out at 40°C for 1 hour.
• Step (3) Subsequently, 1370 g of cyclohexane was added to dilute the reaction solution, and the temperature was raised to 40° C. again. Then, 9.3 g of 2-ethylhexylaldehyde was added and stirred at 40° C. for 1 hour to functionalize some of the lithiated anion active sites.
• Step (4) While controlling the polymerization temperature to 40° C., 190 g of butadiene was successively added and polymerized for 2 hours. After that, 7.0 g of methanol was added to terminate the polymerization reaction to obtain a polymer solution.
• the side chain (b) of the conjugated diene-based graft polymer (G-1) had a number average molecular weight of 5,000, a vinyl content of 75 mol %, and a styrene unit content of 0 mass %.
• Step (5) 450 mL of a Ziegler hydrogenation catalyst (0.095 mmol/L cyclohexane solution) formed from nickel octylate and trimethylaluminum was added to the resulting polymer solution, and the reaction was allowed to proceed for 10 hours under conditions of a hydrogen pressure of 1 MPa and 80°C. to obtain a solution containing a conjugated diene-based graft polymer (G-5).
• a Ziegler hydrogenation catalyst 0.095 mmol/L cyclohexane solution formed from nickel octylate and trimethylaluminum
• Step (6) Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water. After finishing the stirring and confirming that the polymer solution phase and the water phase were separated, the water was separated. After washing, the polymer solution was vacuum-dried at 70° C. for 24 hours to recover a conjugated diene-based graft polymer (G-5).
• the resulting conjugated diene-based graft polymer (G-5) had a weight average molecular weight of 22,000, Mw/Mn of 1.5, a structural unit content derived from styrene of 0% by mass, and a hydrogenation rate of 85 mol.
• the average number of hydroxyl groups bonded to the main chain per polymer molecule is 3, the hydroxyl group concentration is 4.5 mol%, the average number of side chains (b) per polymer molecule is 3, the side chain The density was 4.5 mol%.
• the atom bonded to the side chain (b) contained in the monomer unit that becomes the branched portion is not a hetero atom, and the linking portion containing the atom bonded to the side chain (b) is an aromatic vinyl compound-derived aromatic not the base.
• Table 3 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymer (G-5).
• Example 6 to 10 A conjugated diene-based graft polymer (G-6 ) to (G-8) and (G-11) to (G-12) were obtained.
• TMEDA polar compound used in step (1) was added immediately before adding butadiene after charging cyclohexane and sec-butyllithium into a 5 L autoclave.
• Table 3 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymers (G-6) to (G-8) and (G-11) to (G-12).
• Conjugated diene-based graft polymers (G-10) and (G-13) having no hydroxyl group bonded to the main chain were obtained in the same manner as in Example 5, except for the above.
• TMEDA (polar compound) used in step (1) was added immediately before adding butadiene after charging cyclohexane and sec-butyllithium into a 5 L autoclave.
• Table 3 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymers (G-10) and (G-13).
• Examples 1 to 10 and Comparative Examples 1 to 3 show the types and amounts of each reagent used in steps (1) to (5) in Examples 1 to 10 and Comparative Examples 1 to 3 in Tables 1 and 2 below, Examples 1 to 10 and Comparative Examples 1 to Table 3 shows the molecular specifications and physical properties of the conjugated diene-based graft polymer obtained in 3.
• the lubricating oil additives (viscosity index improvers) comprising the conjugated diene-based graft polymers of Examples 1-10 are the lubricating oil additives (viscosity index improvers) comprising the conjugated diene-based graft polymers of Comparative Examples 1-3. It can be seen that the viscosity index is superior to the index improver). Further, the lubricating oil additives (friction inhibitors) composed of the conjugated diene-based graft polymers of Examples 8 to 10 are the lubricating oil additives (friction inhibitors) composed of the conjugated diene-based graft polymers of Comparative Examples 1 and 3. It can be seen that the friction reduction effect is more excellent.
• the viscosity index improver When the conjugated diene-based graft polymer of the present invention is used as a viscosity index improver, the viscosity index improver has a high viscosity index. Moreover, when the conjugated diene-based graft polymer of the present invention is used as a friction inhibitor, the friction inhibitor has a good friction-reducing effect. Therefore, the conjugated diene-based graft polymer of the present invention is useful, for example, as a lubricating oil additive, such as a viscosity index improver or a friction inhibitor, for lubricating oils used as engine oils and automatic transmission fluids.
• a lubricating oil additive such as a viscosity index improver or a friction inhibitor

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