WO2021132286A1 - 水添共役ジエン系グラフト重合体、及びその製造方法 - Google Patents

水添共役ジエン系グラフト重合体、及びその製造方法 Download PDF

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WO2021132286A1
WO2021132286A1 PCT/JP2020/048051 JP2020048051W WO2021132286A1 WO 2021132286 A1 WO2021132286 A1 WO 2021132286A1 JP 2020048051 W JP2020048051 W JP 2020048051W WO 2021132286 A1 WO2021132286 A1 WO 2021132286A1
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conjugated diene
polymer
graft polymer
based graft
hydrogenated conjugated
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PCT/JP2020/048051
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English (en)
French (fr)
Japanese (ja)
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神原　浩
敦 稲富
順矢 高井
昭明 馬
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株式会社クラレ
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Priority to JP2021567505A priority Critical patent/JP7329622B2/ja
Publication of WO2021132286A1 publication Critical patent/WO2021132286A1/ja

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    • 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
    • C08C19/25—Incorporating silicon atoms into the molecule
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type

Definitions

  • the present invention relates to a hydrogenated conjugated diene-based graft polymer having excellent affinity with polar materials, high stability, and excellent transparency and thermal stability, and a method for producing the same.
  • a polymer having a branch has a higher fluidity than a linear polymer having the same molecular weight, and has an excellent balance between processability and mechanical properties.
  • a method of forming a conjugated diene-based graft polymer by reacting polybutadiene grafted with a silyl chloride group by hydrosilylation with a living polymer having an active terminal of living anionic polymerization that is, hydrogenation of the conjugated diene-based graft polymer.
  • a method for forming a hydrogenated conjugated diene-based graft polymer is known (see Non-Patent Document 1).
  • a conjugated diene-based star polymer in which one or more alkoxy groups and / or hydroxyl groups are bonded on average per one silicon atom has excellent dispersibility of silica (see Patent Document 1). ..
  • Non-Patent Document 1 since the conjugated diene-based graft polymer or hydrogenated conjugated diene-based graft polymer described in Non-Patent Document 1 does not have an alkoxysilyl group or silanol group having an affinity with a polar material, glass, silica, etc. There was room for improvement in the affinity with polar materials. Further, the conjugated diene-based star polymer described in Patent Document 1 has a problem that the stability of the polymer is low because the total content of the alkoxysilyl group and the silanol group capable of causing a condensation reaction is large.
  • the conjugated diene-based graft polymer described in Non-Patent Document 1 contains a halide which is a by-product in the polymer. Halides are required to reduce the content in the polymer due to environmental problems such as causing harmful products to be generated during combustion (see Patent Document 2). Further, it was found that the conjugated diene-based graft polymer described in Non-Patent Document 1 having a high content of halide has problems in transparency and heat resistance. In the above non-patent document, no means for reducing the halide content in the polymer has been studied.
  • the present invention has been made in view of the above circumstances, and is a hydrogenated conjugated diene-based graft polymer having excellent affinity with polar materials, high stability, transparency, and thermal stability.
  • An object of the present invention is to provide a method for producing the hydrogenated conjugated diene-based graft polymer.
  • a side chain composed of a polymer containing a structural unit derived from a monomer is bonded, and at least a part of carbon-carbon double bonds contained in a structural unit derived from a conjugated diene contained in the graft polymer is hydrogenated.
  • the present invention provides the following [1] to [12].
  • [1] In the main chain (a) composed of a polymer containing a structural unit derived from a conjugated diene, A side chain composed of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound via one heteroatom having a valence of 3 or more, which is a branching point.
  • a hydrogenated conjugated diene-based graft polymer to which (b) is bonded and at least a part of carbon-carbon double bonds contained in a structural unit derived from the conjugated diene contained in the graft polymer is hydrogenated.
  • the main chain (a) is connected to the branch point either directly or through a connecting chain.
  • the side chain (b) is directly connected to the branch point.
  • the heteroatom is at least one selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al.
  • At least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group is directly bonded to at least one of the branch points.
  • the average number X of the functional groups (c) directly bonded to the branch point per molecule of the hydrogenated conjugated diene graft polymer and the average number Y of the branch points per molecule of the hydrogenated conjugated diene graft polymer are as follows.
  • A-1) An active terminal polymer represented by the following formula (I) (hereinafter, this polymer is referred to as an active terminal polymer (I)) and PX (I).
  • P represents a polymer chain containing a structural unit derived from at least one monomer selected from the group consisting of conjugated diene and aromatic vinyl compounds
  • X represents the active end of anionic polymerization.
  • a functional group-modified conjugated diene-based polymer having a portion containing a functional group represented by the following formula (II) as a branched chain hereinafter, this polymer is referred to as a functional group-modified conjugated diene-based polymer (F)). Step of reacting to prepare a conjugated diene-based graft polymer
  • V represents an alkoxy group or a hydroxyl group
  • Z is Si, Sn, Ge, Pb, P, B, or Al
  • R 1 is an aryl group having 6 to 12 carbon atoms and a carbon number of carbons. It represents an alkyl group of 1 to 12 or a hydrogen atom
  • N represents the valence of Z
  • n is an integer satisfying the following formula (5)
  • 1 ⁇ n ⁇ N-1 (5) When n is 2 or more, V may be the same or different, and when Nn is 2 or more, R 1 may be the same or different, and when a plurality of branched chains are contained in the main chain.
  • Z may be the same or different.
  • (A-2) A step of inactivating a part of at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene-based graft polymer or the hydrogenated conjugated diene-based graft polymer;
  • [8] The method for producing a hydrogenated conjugated diene-based graft polymer according to [6] or [7], wherein Z in the formula (II) is Si.
  • a hydrogenated conjugated diene-based graft polymer having excellent affinity with a polar material, high stability, and excellent transparency and thermal stability, and a method for producing the same.
  • the hydrogenated conjugated diene-based graft polymer of the present invention (hereinafter, also referred to as hydrogenated conjugated diene-based graft polymer (G)) is In the main chain (a) composed of a polymer containing a structural unit derived from a conjugated diene, A side chain consisting of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound via one heteroatom having a valence of 3 or more, which is a branching point. It has a structure in which (b) is bonded, and has a structure in which (b) is bonded.
  • At least a part of the carbon-carbon double bond contained in the structural unit derived from the conjugated diene contained in the graft polymer is hydrogenated.
  • the main chain (a) is connected to the branch point either directly or through a connecting chain.
  • the side chain (b) is directly connected to the branch point.
  • the heteroatom is at least one selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al.
  • At least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group is directly bonded to at least one of the branch points.
  • the average number Y is the following formula (2); 0 ⁇ (X / Y) ⁇ 1 (2) Satisfy the relationship.
  • the graft polymer means a polymer having a main chain composed of a polymer chain as a trunk and a side chain composed of a polymer chain as a branch, and is a single amount constituting the polymer chain serving as the main chain.
  • the structural unit derived from the body and the structural unit derived from the monomer constituting the polymer chain to be the side chain may be the same or different.
  • the hydrogenated conjugated diene-based graft polymer is a graft polymer containing a structural unit derived from the conjugated diene, and a carbon-carbon double bond contained in the structural unit derived from the conjugated diene. It is a graft polymer to which at least a part of the above is hydrogenated.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention has a main chain (a) composed of a polymer containing a structural unit derived from the conjugated diene.
  • the main chain contained in the hydrogenated conjugated diene-based graft polymer of the present invention refers to the entire structural unit portion derived from all the monomers containing the conjugated diene constituting the main chain.
  • the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention, it is an unmodified precursor of the functional group-modified conjugated diene-based polymer (F) used in the production.
  • the conjugated diene polymer (F') refers to the entire portion derived from the conjugated diene polymer (F').
  • the unmodified conjugated diene polymer (F') contains a structural unit derived from butadiene (1,3-butadiene) having a vinyl bond
  • the main chain (a) is a unit other than a structural unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, a Si atom derived from a residue of a coupling agent) in the polymer chain skeleton. It is preferable not to include a unit having an N atom).
  • a unit other than the structural unit derived from the vinyl monomer is contained in the main clavicle, the bond between the hetero atom and carbon, which is a branching point described later, is broken, or by shearing or heat. Since the clavicle is cleaved, the physical properties tend to deteriorate.
  • the end of the polymer chain, which is the main chain may have a group other than the structural unit derived from the monomer.
  • the main chain (a) contains a structural unit derived from a conjugated diene as a structural unit derived from the monomer constituting the polymer.
  • the conjugated diene include butadiene and isoprene; 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-.
  • conjugated diene other than butadiene and isoprene such as octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadien, 1,3,7-octatriene, milsen, farnesene, and chloroprene.
  • conjugated diene butadiene and isoprene are preferable.
  • the conjugated diene which is a structural unit derived from the conjugated diene, may be used alone or in combination of two or more.
  • the main chain (a) is a structural unit derived from at least one monomer selected from the group consisting of butadiene and isoprene in an amount of 50% by mass or more among the structural units derived from all the monomers constituting the polymer. Is a preferred embodiment.
  • the total content of the structural units derived from butadiene and isoprene is preferably 60 to 100% by mass, preferably 70 to 100% by mass, based on the structural units derived from all the monomers of the main chain (a). Is more preferable.
  • Examples of the structural unit derived from a monomer other than the structural unit derived from butadiene and isoprene that can be contained in the main chain (a) include the structural unit derived from the conjugated diene other than butadiene and isoprene described above, and aromatic vinyl. Examples include structural units derived from compounds.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, and 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, divinyl
  • aromatic vinyl compounds styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
  • the aromatic vinyl compound which is a structural unit derived from the aromatic vinyl compound, may be used alone or in combination of two or more.
  • the content of the structural unit derived from a monomer other than the structural unit derived from butadiene and isoprene in the main chain (a) is preferably 50% by mass or less, more preferably 40% by mass or less. More preferably, it is 30% by mass or less.
  • the structural unit derived from the aromatic vinyl compound is not more than the above range, the processability of the obtained hydrogenated conjugated diene-based graft polymer (G) tends to be improved.
  • the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention, the reactivity is improved when the unmodified conjugated diene-based polymer (F') is modified with a functional group. Tend to do.
  • the weight average molecular weight (Mw) of the main chain (a) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and 3,000 or more and 100. More preferably, it is 000 or less.
  • the Mw of the main chain (a) is, for example, when the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention, the functional group-modified conjugated diene-based polymer (F) described later. ), Or Mw of the unmodified conjugated diene polymer (F') before hydrogenation.
  • Mw is a standard polystyrene-equivalent weight average molecular weight obtained from gel permeation chromatography (GPC) measurements.
  • the vinyl content of the main chain (a) is not particularly limited, but is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 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" is a structural unit derived from a conjugated diene contained in a conjugated diene-based graft polymer (hereinafter, also referred to as a conjugated diene-based graft polymer (G')) before hydrogenation.
  • 4-bond (in the case of other than farnesen) and 1,13-bond (in the case of farnesen) means the total mol% of the structural unit derived from the conjugated diene that is bonded.
  • the vinyl content obtained from the bond form in the structural unit derived from the conjugated diene contained in the polymer before hydrogenation is defined as the vinyl content of the polymer even in the polymer after hydrogenation. To do.
  • the vinyl content of the polymer before hydrogenation is 1,2-bond, 3,4-bond (in the case of other than farnesene), and 3,13-bond (in the case of farnesene) using 1 H-NMR.
  • the vinyl content of the main chain (a) can be designed according to the purpose. For example, when the vinyl content is less than 50 mol%, the glass transition temperature (Tg) of the main chain (a) described later is low. Therefore, the obtained hydrogenated conjugated diene-based graft polymer (G) tends to have excellent fluidity and low temperature characteristics. Further, when it is 50 mol% or more, the heat resistance of the obtained hydrogenated conjugated diene-based graft polymer (G) tends to be excellent.
  • the main chain (a) is composed only of structural units derived from butadiene, the vinyl content of the main chain (a) is set to 25 mol% or more in order to prevent performance deterioration due to crystallization after hydrogenation. Is preferable.
  • the vinyl content of the main chain (a) is, for example, an unmodified conjugated diene-based polymer (F').
  • the desired value can be obtained by controlling the type of solvent used in the production, the polar compound used if necessary, the polymerization temperature, and the like.
  • the glass transition temperature (Tg) of the main chain (a) is derived from the vinyl content of structural units derived from conjugated diene such as butadiene, isoprene, and other conjugated diene, the type of conjugated diene, and monomers other than the conjugated diene. Although it may vary depending on the content of the structural unit to be used, ⁇ 150 to 50 ° C. is preferable, ⁇ 130 to 50 ° C. is more preferable, and ⁇ 130 to 30 ° C. is further preferable. When Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling. In the present invention, Tg is the peak top value of DDSC determined by differential scanning calorimetry (DSC) measurement.
  • DSC differential scanning calorimetry
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention is a side chain (b) composed of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound. ).
  • the side chain (b) contains a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound as a structural unit derived from the monomer constituting the polymer.
  • the specific example of the conjugated diene that can constitute the structural unit derived from the monomer of the side chain (b) is the same as the specific example of the conjugated diene that constitutes the structural unit derived from the monomer of the main chain (a). is there.
  • the conjugated diene which is a structural unit derived from the conjugated diene contained in the side chain (b) butadiene and isoprene are preferable.
  • the conjugated diene may be used alone or in combination of two or more.
  • aromatic vinyl compound that can form a structural unit derived from the monomer of the side chain (b) are those of the aromatic vinyl compound that can form a structural unit derived from the monomer of the main chain (a). It is the same as the specific example. Among these aromatic vinyl compounds, styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
  • the aromatic vinyl compound, which is a structural unit derived from the aromatic vinyl compound may be used alone or in combination of two or more.
  • the side chain (b) is selected from the group consisting of a homopolymer having only a structural unit derived from one conjugated diene or one aromatic vinyl compound, a conjugated diene and an aromatic vinyl compound in the skeleton of the polymer chain.
  • the polymer constituting the side chain (b) may be one kind alone or two or more kinds having different structures.
  • the ratio of structural units derived from the conjugated diene that can form the side chain (b) is not particularly limited and can be designed according to the intended purpose, but is preferably 50% by mass or more, preferably 60% by mass. The above is more preferable, 70% by mass or more is particularly preferable, and 100% by mass may be used.
  • the ratio of the structural units derived from the conjugated diene is 50% by mass or more, the processability of the obtained hydrogenated conjugated diene-based graft polymer (G) tends to be improved.
  • the ratio of structural units derived from the aromatic vinyl compound that can form the side chain (b) is not particularly limited and can be designed according to the intended purpose, but is preferably 50% by mass or more, preferably 60. It is more preferably 70% by mass or more, particularly preferably 70% by mass or more, and may be 100% by mass.
  • the ratio of the structural units derived from the aromatic vinyl compound is 50% by mass or more, the mechanical properties of the obtained hydrogenated conjugated diene-based graft polymer (G) tend to be improved.
  • the side chain (b) is a unit other than a structural unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, a Si atom derived from a residue of a coupling agent) in the polymer chain skeleton. It is preferable not to include a unit having an N atom). If the polymer chain skeleton of the side chain (b) contains a unit other than the structural unit derived from the vinyl monomer, the condition that the bond between the heteroatom and carbon, which is a branching point described later, is broken. Alternatively, the polymer chain skeleton of the side chain (b) is cleaved by shearing or heat, so that the physical properties tend to deteriorate. The end of the polymer chain to be the side chain may have a group other than the structural unit derived from the monomer.
  • a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, a Si atom derived from a residue of a coupling agent
  • the weight average molecular weight (Mw) of the side chain (b) is preferably 1,000 or more and 200,000 or less, more preferably 2,000 or more and 150,000 or less, and 3,000 or more and 100,000 or less. The following is more preferable.
  • the Mw of the side chain (b) is, for example, hydrogenated from the active terminal polymer (I) described later when the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention. It is Mw in the previous state. When the Mw of the side chain (b) is within the above range, the process passability during manufacturing tends to be excellent and the economic efficiency tends to be good.
  • the vinyl content of the side chain (b) is not particularly limited, but is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 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) is, for example, when the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention, the vinyl content of the active terminal polymer (I) before hydrogenation, which will be described later. 1 Calculate from the H-NMR spectrum in the same manner as in the case of the main chain (a).
  • the vinyl content of the side chain (b) can be designed according to the purpose. For example, when the vinyl content is less than 50 mol%, the glass transition temperature (Tg) of the side chain (b) described later is low. Therefore, the obtained hydrogenated conjugated diene-based graft polymer (G) tends to have excellent fluidity and low temperature characteristics. Further, when it is 50 mol% or more, the heat resistance of the obtained hydrogenated conjugated diene-based graft polymer (G) tends to be excellent.
  • the side chain (b) is composed only of structural units derived from butadiene, the vinyl content of the side chain (b) is set to 25 mol% or more in order to prevent performance deterioration due to crystallization after hydrogenation. Is preferable.
  • the vinyl content of the side chain (b) is, for example, the active terminal which is a component of the side chain (b) when the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention.
  • the desired value can be obtained by controlling the type of solvent used in producing the polymer (I), the polar compound used as necessary, the polymerization temperature, and the like.
  • the glass transition temperature (Tg) of the side chain (b) can vary depending on the vinyl content of the structural unit derived from the conjugated diene, the type of the conjugated diene, the content of the structural unit derived from a monomer other than the conjugated diene, and the like. However, ⁇ 150 to 50 ° C. is preferable, ⁇ 130 to 50 ° C. is more preferable, and ⁇ 130 to 30 ° C. is further preferable. When Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling.
  • the side chain (b) is bonded to the main chain (a) via one heteroatom having a valence of 3 or more, which is a branching point.
  • a hydrogenated conjugated diene graft polymer (G) to which at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group is bonded to at least one of the branching points.
  • the main chain (a) is bonded to the branch point directly or through a connecting chain
  • the side chain (b) is directly bonded to the branch point
  • the functional group (c) is directly bonded to the branch point.
  • bonded directly to the branch point means that the branch point is directly bonded to the structural unit portion derived from the monomer constituting the main chain.
  • a branch point and a bond through a connecting chain means that one end of the connecting chain is bound to a structural unit portion derived from a monomer constituting the main chain, and the branch point is directly connected to the other end of the connecting chain. It means that they are combined.
  • the case represented by the following formula (III-1) is a case where the main chain is directly bonded to the branch point.
  • the case represented by the following formula (III-2) is the case where the main chain is connected to the branch point through the connecting chain.
  • Z 0 is a heteroatom serving as a branch point
  • R 2a is a connecting chain.
  • R 2a is a divalent organic group, an alkylene group which may have a hetero atom is preferable.
  • the wavy line portion is the main chain (a)
  • V is the functional group (c)
  • Z 1 is the branch point
  • P is the side chain (b)
  • R 2b is connected. It is a chain.
  • V represents an alkoxy group or a hydroxyl group
  • Z 1 is Si, Sn, Ge, Pb, P, B, or Al
  • R 2b has a heteroatom.
  • It represents an alkylene group having 1 to 12 carbon atoms which may be used
  • R 3 represents an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a hydrogen atom
  • P represents a conjugated diene and an aromatic group.
  • a polymer chain containing a structural unit derived from at least one monomer selected from the group consisting of vinyl compounds is shown.
  • N represents the valence of Z, and m and n are integers that independently satisfy the following equation (6); 0 ⁇ m ⁇ N-1, 0 ⁇ n ⁇ N-1 (6)
  • P may be the same or different
  • V may be the same or different
  • R 3 may be the same.
  • Z 1 may be the same or different when a plurality of branch points are included in the main chain.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention contains V (functional group (c)) and P (side chain (b)) while satisfying the relationship of the above formula (6). There is a need.
  • Z 1 (m is 0) to which the side chains are not bonded is 0.
  • Z 1 can be included, but even in that case, Z 1 is defined as a branch point.
  • the above branch point consists of one heteroatom, and the heteroatom is a heteroatom having a valence of 3 or more.
  • the heteroatom having a valence of 3 or more as a branching point is at least one selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al. Among these heteroatoms, Si, Sn, and B are preferable, and Si is more preferable.
  • the functional group (c) serving as the group V is at least one selected from the group consisting of an alkoxy group and a hydroxyl group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like.
  • a methoxy group, an ethoxy group, and a hydroxyl group are preferable from the viewpoint of affinity with a polar material.
  • the functional group (c) may be a single group of one type or a plurality of groups of two or more types.
  • R 3 in the above formulas (III-3) and (III-4) represents an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a hydrogen atom.
  • alkyl groups having 1 to 6 carbon atoms are preferable, and n-butyl groups, sec-butyl groups, n-propyl groups, isopropyl groups, ethyl groups, and methyl groups are more preferable.
  • R 3 may be a single group of one type or a plurality of groups of two or more types.
  • alkylene group having 1 to 12 carbon atoms having a heteroatom capable of becoming R 2b an alkylene group having 1 to 12 carbon atoms having S is preferable, and SR 2b' (R 2b'is an alkylene group having 1 to 12 carbon atoms. Shown) is more preferable.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention when focusing on a hetero atom which is a branch point contained in the graft polymer, the valence of the hetero atom is N, and one branch point is When the average number of side chains (b) directly bonded to each other is B and the average number of the functional groups (c) bonded to one branch point is C, the relationship of the following formula (1) is satisfied. become. By satisfying this condition, the branch point is bonded to the main chain (a) directly or through the connecting chain, and the hydrogenated conjugated diene graft polymer (G) of the present invention has at least the side chain (b).
  • the functional group (c) will be included. N-1 ⁇ B + C, B> 0, C> 0 (1)
  • the hydrogenated-conjugated diene-based graft polymer (G) of the present invention includes the average number X of functional groups (c) directly bonded to the above-mentioned branch point per molecule of the hydrogenated-conjugated diene-based graft polymer (G) and hydrogenation.
  • the average number Y of branch points per molecule of the conjugated diene-based graft polymer (G) satisfies the relationship of the following formula (2).
  • the above (X / Y) is preferably in the range of 0.01 or more and 0.99 or less, and preferably in the range of 0.01 or more and 0.9 or less. It is more preferable, and it is particularly preferable that the range is 0.01 or more and 0.5 or less.
  • (X / Y) (the average number of functional groups (c) per branch point contained in the hydrogenated conjugated diene-based graft polymer (G)) is, for example, when Z is Si. , 29 Si-NMR of hydrogenated conjugated diene-based graft polymer (G) is obtained from the measurement results.
  • the average number Y of branch points per molecule of the hydrogenated conjugated diene graft polymer (G) is measured by an inductively coupled plasma mass spectrometer (ICP-MS). Calculated from the following formula (7) using the content (mass%) of specific heteroatoms (Si, Sn, Ge, Pb, P, B, and Al) and the number average molecular weight (Mn) converted to standard polystyrene. ..
  • the average number X of functional groups (c) directly bonded to the above-mentioned branch point per molecule of the hydrogenated conjugated diene-based graft polymer (G) is as follows. It is preferable to satisfy the relationship of the formula (3). 0 ⁇ X ⁇ 10 (3)
  • the average number X of the functional groups (c) is calculated by the method described later. When the above X is 0, the hydrogenated conjugated diene graft polymer (G) tends to be inferior in affinity with the polar material, and when the above X exceeds 10, the hydrogenated conjugated diene graft polymer (G) tends to be inferior. ) Tends to be less stable.
  • X is preferably in the range of 0.01 or more and 9.9 or less, more preferably 0.02 or more and 9 or less, and 0. It is particularly preferable that the range is 05 or more and 5 or less.
  • the average number X of the functional groups (c) directly bonded to the branch point per molecule of the hydrogenated conjugated diene graft polymer (G) is the same as that of the hydrogenated conjugated diene graft polymer (G). It is determined by using the average number (X / Y) of functional groups (c) per contained branch point and the average number Y of branch points per molecule of the hydrogenated conjugated diene-based graft polymer (G).
  • the number of side chains (b) and the number of functional groups (c) directly bonded to the branch point are determined when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention.
  • the stability of the hydrogenated conjugated diene-based graft polymer (G) can be evaluated by, for example, a change in appearance and formation of an insoluble matter (gelled product) when stored for a long period of time under normal temperature and pressure. It is also possible to evaluate the hydrogenated conjugated diene-based graft polymer (G) under conditions that promote the condensation reaction of the alkoxysilyl group or silanol group by heating and reducing the pressure.
  • a hydrogenated conjugated diene-based graft polymer (G) or a polymer composition containing a hydrogenated conjugated diene-based graft polymer (G) is applied onto a glass substrate, and the polymer composition is coated. After curing by heating for a certain period of time, it can be evaluated by measuring the peel strength and performing a diene test. Further, the reactivity and affinity with polar materials such as glass and silica can be evaluated by the condensation reactivity of the alkoxysilyl group or the silanol group.
  • the average number of side chains (b) directly bonded to the above-mentioned branch point per molecule of the hydrogenated conjugated diene-based graft polymer (G) is W, water.
  • W / Y it is preferable that (W / Y) satisfies the relationship of the following formula (4). 0.5 ⁇ (W / Y) (4)
  • the above (W / Y) is more preferably 0.6 or more (0.6 ⁇ (W / Y)), and further preferably 0.8 or more (0.8 ⁇ (W / Y)).
  • the average number W of side chains (b) directly bonded to the branch point per molecule of the hydrogenated conjugated diene-based graft polymer (G) is determined by the production method of the present invention according to the hydrogenated conjugated diene-based graft weight.
  • the average number Y of branching points per molecule of the hydrogenated conjugated diene-based graft polymer (G) is calculated by the method described above. If the above (W / Y) is less than 0.5, the fluidity of the hydrogenated conjugated diene-based graft polymer (G) is lowered, and the balance between processability and mechanical properties tends to be poor.
  • the degree of branching of the hydrogenated conjugated diene-based graft polymer (G) is the same as the radius of gyration (R) with respect to the weight average molecular weight (Mw) of the hydrogenated conjugated diene-based graft polymer (G) by the absolute method.
  • R radius of gyration
  • Mw weight average molecular weight of the hydrogenated conjugated diene-based graft polymer
  • the random coil chain of a normal linear polymer shows a value of about 0.6 to 0.8 for both ⁇ s and ⁇ ⁇ , and if it is less than 0.6, the existence of a branched chain is suggested.
  • the value of ⁇ s or ⁇ ⁇ of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is preferably less than 0.6, more preferably 0.55 or less, and more preferably 0.50 or less. Is even more preferable.
  • the log-log plot of the weight average molecular weight (Mw) and the radius of gyration (R) or the intrinsic viscosity ( ⁇ ) by the absolute method of the hydrogenated conjugated diene graft polymer (G) is obtained by, for example, the SEC-MALS-VISCO method. can do.
  • the SEC-MALS-VISCO method is a type of liquid chromatography (SEC) that separates polymer chains according to the difference in molecular size (hydrodynamic volume), and is a differential refractometer (RI) and a polygonal light scattering detector.
  • the radius of gyration and intrinsic viscosity of each molecular weight of the polymer solution size-sorted by SEC can be calculated.
  • the value of ⁇ s or ⁇ ⁇ of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is in the above range, the fluidity of the hydrogenated conjugated diene-based graft polymer (G) is improved, and the processability is improved. It tends to have an excellent balance of mechanical properties.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention has an average number W of side chains (b) directly bonded to the above-mentioned branch point per molecule of the hydrogenated conjugated diene-based graft polymer (G) of 1 or more. Is more preferable, 2 or more is more preferable, and 3 or more is further preferable.
  • the average number W of the side chains (b) is calculated by the method described above. If the average number W of the side chains (b) is less than 1, the fluidity of the hydrogenated conjugated diene-based graft polymer (G) tends to decrease, and the balance between processability and mechanical properties tends to be poor.
  • the combination of the polymer that becomes the main chain (a) and the polymer that becomes the side chain (b) contained in the hydrogenated conjugated diene-based graft polymer (G) is not particularly limited and may be the same or different. It is possible to design according to.
  • the difference between the polymer serving as the main chain (a) and the polymer serving as the side chain (b) means that at least one selected from the group consisting of the following (i) to (iv) is different.
  • the molecular weight of the polymer that becomes the main chain (a) is different from the molecular weight of the polymer that becomes the side chain (b).
  • the type or combination of structural units derived from the monomer of the polymer serving as the main chain (a) is the type or combination of structural units derived from the monomer of the polymer serving as the side chain (b). Different from the combination of types.
  • the main chain (a) and the side chain (b) each contain a structural unit derived from a plurality of monomers of the same type, the monomer of the polymer to be the main chain (a) is used.
  • the derived structural unit composition ratio is different from the structural unit composition ratio derived from the monomer of the polymer having the side chain (b).
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention is at least one selected from the group consisting of butadiene and isoprene in an amount of 50% by mass or more among the structural units derived from all the monomers constituting the polymer.
  • One embodiment is preferably a structural unit derived from one monomer.
  • the total content of the structural units derived from butadiene and isoprene is more preferably 60 to 100% by mass with respect to the structural units derived from all the monomers of the hydrogenated conjugated diene-based graft polymer (G). It is more preferably 70 to 100% by mass.
  • the content of structural units derived from monomers other than butadiene and isoprene in the hydrogenated conjugated diene-based graft polymer (G) of the present invention is preferably 50% by mass or less, preferably 40% by mass or less. Is more preferable, and 30% by mass or less is further preferable.
  • the structural unit derived from the aromatic vinyl compound is not more than the above range, the processability of the hydrogenated conjugated diene-based graft polymer (G) of the present invention tends to be improved.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention at least a part of carbon-carbon double bonds contained in the structural unit derived from the conjugated diene contained in the graft polymer is hydrogenated.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention is included in the structural unit derived from the conjugated diene in the conjugated diene-based graft polymer (G') before hydrogenation from the viewpoint of heat resistance and weather resistance.
  • 50 mol% or more of the carbon-carbon double bond is preferably hydrogenated, 80 mol% or more is more preferably hydrogenated, and 90 mol% or more is hydrogenated. More preferred.
  • the hydrogenation rate is usually 100 mol% or less.
  • the hydrogenation rate may be substantially 100 mol% (that is, substantially complete hydrogenation).
  • the hydrogenation rate was calculated by using 1 H-NMR to calculate the content of carbon-carbon double bonds contained in the structural unit derived from the conjugated diene in the polymer before and after hydrogenation. It is a value obtained from the content.
  • the weight average molecular weight (Mw) of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is preferably 5,000 or more and 2,000,000 or less, which is 30,000 or more and 1,500, It is preferably 000 or less, and more preferably more than 100,000 and 1,000,000 or less.
  • Mw of the hydrogenated conjugated diene-based graft polymer (G) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good. Further, the processability of the polymer composition containing the hydrogenated conjugated diene-based graft polymer (G) tends to be improved.
  • the molecular weight distribution (Mw / Mn) of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, and 1.0 to 5. 0 is more preferable, and 1.0 to 2.0 is particularly preferable.
  • Mw / Mn means a number average molecular weight
  • Mn is a standard polystyrene-equivalent number average molecular weight obtained from GPC measurement.
  • the molecular weight distribution (Mw / Mn) means the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene obtained by GPC measurement.
  • the vinyl content of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is not particularly limited, but is preferably 90 mol% or less, more preferably 80 mol% or less, and 70 mol% or less. More preferred.
  • the vinyl content of the hydrogenated conjugated diene-based graft polymer (G) is preferably 0.5 mol% or more, more preferably 1 mol% or more.
  • the vinyl content of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is the same as that of the main chain (a) according to the 1 H-NMR spectrum of the conjugated diene-based graft polymer (G') before hydrogenation. And calculate.
  • the vinyl content of the hydrogenated conjugated diene-based graft polymer (G) can be designed according to the purpose. For example, when the vinyl content is less than 50 mol%, the hydrogenated conjugated diene-based graft polymer (G) ), The glass transition temperature (Tg) tends to be low, and the fluidity and low temperature characteristics tend to be excellent. Further, when it is 50 mol% or more, the heat resistance of the hydrogenated conjugated diene-based graft polymer (G) tends to be excellent.
  • the hydrogenated conjugated diene-based graft polymer (G) is composed of only structural units derived from butadiene as structural units derived from the monomer, in order to prevent performance deterioration due to crystallization after hydrogenation.
  • the vinyl content of the hydrogenated conjugated diene-based graft polymer (G) is preferably 25 mol% or more.
  • the glass transition temperature (Tg) of the hydrogenated conjugated diene-based graft polymer (G) is the vinyl content of structural units derived from the conjugated diene such as butadiene, isoprene and other conjugated diene, the type of the conjugated diene, and other than the conjugated diene. Although it may vary depending on the content of the structural unit derived from the monomer, it is preferably ⁇ 150 to 50 ° C., more preferably ⁇ 130 to 50 ° C., and even more preferably ⁇ 130 to 30 ° C. When Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling.
  • the mass ratio (a) / (b) of the main chain (a) and the side chain (b) in the hydrogenated conjugated diene-based graft polymer (G) of the present invention is 0.05 / 99.95 to 90/10.
  • the range is preferred, the range of 0.1 / 99.9 to 80/20 is more preferred, and the range of 0.5 / 99.5 to 70/30 is even more preferred.
  • the mass ratio of the main chain to the side chain is in the above range, the processability of the polymer composition containing the hydrogenated conjugated diene-based graft polymer (G) tends to be improved.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention has a total amount of catalyst residue derived from the polymerization catalyst, hydrogenation catalyst (hydrogenated catalyst), etc. used for its production in the range of 0 to 500 ppm in terms of metal. It is preferable to be in.
  • an organic alkali metal such as an organic lithium compound described later is used as a polymerization catalyst for producing a conjugated diene-based graft polymer (G') before hydrogenation
  • the alkali metal such as lithium is used.
  • the alkali metal such as lithium is used.
  • the hydrogenation catalyst when a Ziegler-based catalyst is used as the hydrogenation catalyst, nickel or aluminum may be contained.
  • the total amount of the catalyst residue of the hydrogenated conjugated diene-based graft polymer (G) is more preferably 0 to 300 ppm, still more preferably 0 to 200 ppm in terms of metal.
  • the amount of catalyst residue can be measured by using, for example, an inductively coupled plasma mass spectrometer (ICP-MS) or a polarized Zeeman atomic absorption spectrophotometer.
  • the hydrogenated conjugated diene-based graft polymer (G) As a method of setting the amount of the catalyst residue of the hydrogenated conjugated diene-based graft polymer (G) to such a specific amount, the hydrogenated conjugated diene-based graft polymer (G) is purified and the catalyst residue is sufficiently removed.
  • the method etc. can be mentioned.
  • As a method for purification cleaning with water or warm water, an acidic aqueous solution, an organic solvent typified by methanol, acetone, or the like, or cleaning with supercritical fluid carbon dioxide is preferable.
  • the cleaning efficiency can be further improved by using an acidic aqueous solution for cleaning.
  • the acid to be used examples include 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; monovalents such as carbonic acid and phosphoric acid.
  • a polyvalent weak acid is preferable.
  • the number of washings is preferably 1 to 20 times, more preferably 1 to 10 times.
  • the cleaning temperature is preferably 20 to 100 ° C, more preferably 40 to 90 ° C.
  • the amount of polymerization catalyst required can be reduced by removing impurities that inhibit polymerization by distillation or an adsorbent before the polymerization reaction to increase the purity of the monomer and then performing polymerization.
  • the amount of catalyst residue can be reduced.
  • the hydrogenated conjugated diene-based graft polymer (G) of the present invention preferably has a halogen content of 0 to 1,000 ppm.
  • a silyl chloride-modified conjugated diene-based polymer is used as the functional group-modified conjugated diene-based polymer (F) for producing a hydrogenated conjugated diene-based graft polymer (G)
  • a reference halogen is used. Becomes chlorine.
  • the halogen content is in the above range, the transparency, heat resistance, and weather resistance tend to be good.
  • the halogen content of the hydrogenated conjugated diene-based graft polymer (G) is more preferably 0 to 500 ppm, still more preferably 0 to 100 ppm.
  • the halogen content can be measured by using, for example, combustion ion chromatography.
  • the conjugated diene polymer (F) include a method of using an alkoxysilane-modified conjugated diene polymer that does not generate a halide as a by-product.
  • the method for producing the hydrogenated conjugated diene-based graft polymer (G) of the present invention is not particularly limited.
  • a macromonomer containing a structural unit derived from at least one monomer selected from the group consisting of conjugated diene and aromatic vinyl compound at least one selected from the group consisting of conjugated diene and aromatic vinyl compound.
  • a method for producing a polymer and hydrogenating the obtained conjugated diene-based graft polymer to produce a hydrogenated conjugated diene-based graft polymer (a simple reaction with a polymerizable functional group contained in a macromonomer and a macromonomer).
  • the part derived from the polymer chain obtained from the polymer is the main chain / the part derived from the polymer chain other than the part derived from the compound containing the polymerizable functional group contained in the macromonomer is the side chain); (Ii) In the presence of tetramethylethylenediamine, a polymer containing a structural unit derived from conjugated diene is reacted with an organic alkali metal compound to obtain a polymer having a metal active moiety, and then the metal.
  • a conjugated diene-based graft polymer was prepared by polymerizing a monomer containing at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound from the active moiety to prepare a conjugated diene-based graft polymer, and the obtained conjugated diene-based graft polymer was obtained.
  • a method for producing a hydrogenated conjugated diene-based graft polymer (a portion derived from the polymer chain contained in the polymer to be reacted with the organic alkali metal compound was obtained by polymerizing from the main chain / metal active portion.
  • the part derived from the polymer chain is the side chain); (Iii) Containing a structural unit derived from a conjugated diene and having two active terminals, and a structural unit derived from at least one monomer selected from the group consisting of the conjugated diene and an aromatic vinyl compound. , And a mixture of polymers having one active terminal was prepared, and a coupling agent having 3 or more reactive sites was added to the mixture and reacted to prepare a conjugated diene-based graft polymer, and the obtained conjugate was obtained.
  • a method for producing a hydrogenated conjugated diene-based graft polymer by hydrogenating a diene-based graft polymer (the portion derived from the polymer chain contained in the polymer having two active ends is the main chain / one active end. The part derived from the polymer chain contained in the polymer has a side chain); (Iv) A polymer containing a structural unit derived from a conjugated diene synthesized in advance is modified with a functional group to prepare a functional group-modified polymer, and the functional group contained in the functional group-modified polymer and the conjugated diene and aromatics are prepared.
  • a conjugated diene-based graft polymer was prepared by reacting with an active terminal of a polymer obtained by polymerizing a monomer containing at least one monomer selected from the group consisting of vinyl compounds to prepare a conjugated diene-based graft polymer, and the obtained conjugated diene-based graft weight was obtained.
  • a method for producing a hydrogenated conjugated diene-based graft polymer by hydrogenating the coalescence (a polymer chain contained in a polymer in which a portion derived from the polymer chain contained in the functional group-modified polymer has a main chain / active terminal. The part derived from is the side chain); and the like.
  • the weight average molecular weight and vinyl content of the main chain and side chains of the hydrogenated conjugated diene-based graft polymer (G), the number of side chains, etc. can be freely controlled, and a desired functional group is used.
  • a production method including the following steps (A-1), (B), and (C) is preferable.
  • P represents a polymer chain containing a structural unit derived from at least one monomer selected from the group consisting of conjugated diene and aromatic vinyl compounds, and X represents the active end of anionic polymerization. .
  • V represents an alkoxy group or a hydroxyl group
  • Z is Si, Sn, Ge, Pb, P, B, or Al
  • R 1 is an aryl group having 6 to 12 carbon atoms and a carbon number of carbons. It represents an alkyl group of 1 to 12 or a hydrogen atom
  • N represents the valence of Z
  • n is an integer satisfying the following formula (5); 1 ⁇ n ⁇ N-1 (5)
  • V may be the same or different
  • Nn is 2 or more
  • R 1 may be the same or different, and when a plurality of branched chains are contained in the main chain.
  • Z may be the same or different.
  • the branched chain of the functional group-modified conjugated diene-based polymer (F) means a portion other than the main chain of the functional group-modified conjugated diene-based polymer (F), and this main chain is a conjugated diene-based graft. Similar to the main chain (a) in the polymer, it refers to the entire structural unit portion derived from all the monomers containing the conjugated diene constituting the main chain.
  • the active terminal polymer (I) used in the above step (A-1) can be produced by using a known polymerization method. For example, an anionically polymerizable active metal or active metal compound is used as an initiator in a solvent inert to the polymerization terminal, and the monomer is anionically polymerized in the presence of a polar compound, if necessary. Coalescence (I) can be obtained. The P of the active terminal polymer (I) becomes the side chain (b') of the conjugated diene-based graft polymer (G').
  • the monomer as a structural unit derived from the monomer constituting the active terminal polymer (I), description of preferred embodiments, etc., and the monomer derived from the monomer contained in the active terminal polymer (I).
  • the description of specific examples and preferred embodiments of the structural unit is the same as the description of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G).
  • an organic alkali metal compound is preferable, and an organic lithium compound is more preferable.
  • 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; benzene. , Aromatic hydrocarbons such as toluene and xylene.
  • a polar compound may be added during the above anionic polymerization.
  • Polar compounds are usually used in anionic polymerization to adjust the microstructure (vinyl content) of the conjugated diene moiety without inactivating the reaction.
  • the polar compound 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 usually 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., and more preferably in the range of 10 to 90 ° C.
  • the polymerization mode may be either a batch type or a continuous type.
  • the P of the active terminal polymer (I) finally becomes the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G) of the present invention through the hydrogenation step described later.
  • the description of the weight average molecular weight (Mw) of P of the active terminal polymer (I), the vinyl content, the preferred embodiment of Tg and the like is described in the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G) of the present invention. Similar to that for.
  • the functional group-modified conjugated diene-based polymer (F) can be obtained, for example, by modifying the unmodified conjugated diene-based polymer (F') with a functional group in the modification step described later.
  • the method for producing the unmodified conjugated diene polymer (F') is not particularly limited, but for example, an emulsion polymerization method and a solution polymerization method are preferable, and a solution polymerization method is more preferable from the viewpoint of the molecular weight distribution of the obtained polymer. ..
  • the portion of the functional group-modified conjugated diene-based polymer (F) other than the functional group-modified portion becomes the main chain (a') of the conjugated diene-based graft polymer (G').
  • conjugated diene which is a structural unit derived from the monomer constituting the unmodified conjugated diene polymer (F'), and monomers other than conjugated diene.
  • the description of specific examples, preferred examples, suitable contents and the like of the (aromatic vinyl compound) is the same as the description regarding the main chain (a) of the hydrogenated conjugated diene-based graft polymer (G). Further, the description of the weight average molecular weight (Mw), vinyl content, preferred embodiment of Tg of the unmodified conjugated diene polymer (F') and the like is described in the main chain (a) of the hydrogenated conjugated diene graft polymer (G). It is the same as the explanation about.
  • emulsification polymerization method which is an example of the method for producing an unmodified conjugated diene polymer (F')
  • a known or 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 polymerization is carried out with a radical polymerization initiator.
  • Examples of the emulsifier include long-chain fatty acid salts having 10 or more carbon atoms and rosin salts.
  • Examples of the long-chain fatty acid salt 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 initiator examples include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
  • a chain transfer agent may be used to adjust the molecular weight of the obtained unmodified conjugated diene polymer (F').
  • the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, turpinolene, ⁇ -terpinene, ⁇ -methylstyrene dimer and the like.
  • the temperature of emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator used, but is usually in the range of 0 to 100 ° C, preferably in the range of 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 inhibitor.
  • 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 if necessary.
  • unreacted monomers are removed from the obtained latex as needed, and then salts such as sodium chloride, calcium chloride and potassium chloride are used as coagulants, and if necessary, nitrates, sulfuric acid and the like are added.
  • the unmodified conjugated diene polymer (F') is coagulated while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then the polymer is recovered by separating the dispersion medium. Then, the unmodified conjugated diene polymer (F') is obtained by washing with water, dehydrating, and then drying.
  • the latex and the extension oil prepared as an emulsified dispersion may be mixed and recovered as an oil-expanded unmodified conjugated diene polymer (F').
  • a known or known method can be applied. For example, a single amount containing a conjugated diene 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. Polymerize the body.
  • 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; benzene, Examples include aromatic hydrocarbons such as toluene and xylene.
  • an anionic polymerizable active metal or active metal compound is preferable, and an anionic polymerizable active metal compound is more preferable.
  • anionic polymerizable active metals examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and lanthanoid rare earth metals such as lanthanum and neodymium. .. Among these, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
  • an organic alkali metal compound is preferable.
  • the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stillbenlithium; , 1,4-Dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other polyfunctional organic lithium compounds; sodium naphthalene, potassium naphthalene and the like.
  • an organic lithium compound is preferable, and an organic monolithium compound is more preferable.
  • the amount of the initiator used can be appropriately set according to the melt viscosity, molecular weight, etc. of the unmodified conjugated diene polymer (F') and the functionally modified conjugated diene polymer (F), but the total amount including the conjugated diene is included. It is usually used in an amount of 0.01 to 3 parts by mass with respect to 100 parts by mass of the monomer.
  • the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine or dibenzylamine. ..
  • Polar compounds are usually used in anionic polymerization to adjust the microstructure (vinyl content) of the conjugated diene site without inactivating the reaction.
  • the polar compound 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 usually 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., and more preferably in the range of 10 to 90 ° C.
  • the polymerization mode may be either a batch type or a continuous type.
  • the polymerization reaction of the above solution polymerization can be stopped 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 an unmodified conjugated diene polymer (F'), or the polymerization reaction solution is washed with water, separated, and dried.
  • a modified conjugated diene polymer (F') can be isolated.
  • the unmodified conjugated diene-based polymer (F') thus obtained may be modified with a functional group as it is, but is included in the structural unit derived from the conjugated diene in the conjugated diene-based polymer. After hydrogenating at least a part of the carbon-carbon double bond to be hydrogenated by the hydrogenation method described later, modification may be carried out.
  • the functional group-modified conjugated diene polymer (F) having a moiety containing a functional group represented by the above formula (II) as a branched chain.
  • the method for producing the above is not particularly limited, but from the viewpoint of introducing a functional group having a preferable structure, for example, a mercapto group (-SH) is added to the carbon-carbon double bond contained in the unmodified conjugated diene polymer (F').
  • a method of introducing a functional group derived from an alkoxysilane compound by subjecting a compound having () to a radical addition reaction, a carbon-carbon double bond contained in an unmodified conjugated diene polymer (F') is a platinum compound-containing catalyst.
  • a method of introducing a functional group derived from an alkoxysilane compound by hydrosilylation in the presence of a co-catalyst used as needed can be mentioned.
  • a method in which a compound having a mercapto group (-SH) is subjected to a radical addition reaction is preferable, and the obtained functional group-modified conjugated diene system weight is preferable.
  • a method of introducing a functional group derived from an alkoxysilane compound by hydrosilylation is preferable.
  • a functional group derived from an alkoxysilane compound is introduced by radically adding a compound having a mercapto group (-SH) to a carbon-carbon double bond contained in the unmodified conjugated diene-based polymer (F').
  • a method a method in which a silane compound (IV) represented by the following formula (IV) is radically added to a carbon-carbon double bond contained in an unmodified conjugated diene-based polymer (F') is preferable.
  • R 4 represents a divalent alkylene group having 1 to 6 carbon atoms
  • R 5 and R 6 are independently an aryl group having 6 to 12 carbon atoms and an alkyl having 1 to 12 carbon atoms, respectively.
  • n is an integer of 1 to 3
  • R 5 may be the same or different
  • R 6 may be the same. It may be different.
  • silane compound (IV) examples include mercaptomethylenemethyldiethoxysilane, mercaptomethylenetriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, and 2-.
  • the mercapto group (-SH) of the silane compound (IV) is derived from the silane compound (IV) by a radical addition reaction to the carbon-carbon double bond contained in the unmodified conjugated diene polymer (F').
  • a functional group-modified conjugated diene polymer (F) having a functional group to be treated, specifically, a partial structure represented by the following formula (V) as a functional group can be obtained.
  • the method for adding the silane compound (IV) to the unmodified conjugated diene polymer (F') is not particularly limited, and for example, the silane compound (IV) is added to the unmodified conjugated diene polymer (F'). Further, if necessary, a method of adding a radical generator and heating in the presence or absence of an organic solvent can be adopted.
  • the radical generator to be used is not particularly limited, and commercially available organic peroxides, azo compounds, hydrogen peroxide and the like can be used.
  • organic peroxide examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, and 1,1-bis (t-butylperoxy).
  • azo compound examples include 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), and 2,2'-azobis (2-methylbutyronitrile). , 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2- (2-imidazoline) -2-yl) propane), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (2-hydroxymethylpropion) Nitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobis (2-methylpropionate), 2-cyano-2-propylazoformamide, 2-phenylazo-4- Examples thereof include methoxy-2,4-dimethylvaleronitrile.
  • the radical generator may be used alone or in combination of two or more.
  • Examples of the organic solvent used in the above method generally include a hydrocarbon solvent and a halogenated hydrocarbon solvent.
  • hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • an antiaging agent may be added from the viewpoint of suppressing side reactions.
  • Preferred anti-aging agents used at this time include, for example, 2,6-dit-butyl-4-methylphenol (BHT), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4.
  • the amount of the antiaging agent added is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene polymer (F').
  • the temperature in the reaction of adding the silane compound (IV) to the unmodified conjugated diene polymer (F') is preferably 10 to 200 ° C, more preferably 50 to 180 ° C.
  • the reaction time is preferably 1 to 200 hours, more preferably 1 to 100 hours, still more preferably 1 to 50 hours.
  • R 7 and R 8 independently represent an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, where n is an integer of 1 to 3 and n is. If it is 2 or more, R 7 may be the same or different, and if 3-n is 2 or more, R 8 may be the same or different.
  • silane compound (VI) examples include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane. These silane compounds may be used alone or in combination of two or more.
  • a functional group-modified conjugated diene polymer (F) having a partial structure represented by the following formula (VII) as a functional group can be obtained.
  • the platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and is, for example, platinum chloride, an alcohol solution of platinum chloride, platinum-1,3-divinyl-1,1,3,3-tetramethyl. Toluene or xylene solution of disiloxane complex, tetraxtriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadien platinum, etc., platinum-carbon, platinum-alumina, platinum- Examples thereof include a carrying catalyst such as silica.
  • a zero-valent platinum complex is preferable, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferable.
  • the amount of the platinum compound-containing catalyst used is not particularly limited, but from the viewpoints of reactivity, productivity, etc., the amount of platinum atoms contained in 1 mol of the silane compound (VI) is 1 ⁇ 10 -7.
  • the amount to be ⁇ 1 ⁇ 10 ⁇ 2 mol is preferable, and the amount to be 1 ⁇ 10 -7 to 1 ⁇ 10 -3 mol is more preferable.
  • the co-catalyst in the above reaction it is preferable to use one or more selected from ammonium salts of inorganic acids, acid amide compounds and carboxylic acids.
  • ammonium salt of the inorganic acid examples include ammonium chloride, ammonium sulfate, ammonium amidosulfate, ammonium nitrate, monoammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diaphosphate, ammonium carbonate, and ammonium hydrogencarbonate. , Ammonium sulfide, ammonium borate, ammonium borofluoride and the like. Among these, ammonium salts of inorganic acids having a pKa of 2 or more are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.
  • Examples of the acid amide compound include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, acrylamide, malonamide, succinamide, maleamide, fumalamide, benzamide, phthalamide, palmitate amide and stearate amide. Can be mentioned.
  • carboxylic acid examples include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, and glycolic acid.
  • formic acid, acetic acid and lactic acid are preferable, and acetic acid is more preferable.
  • the amount of the co-catalyst used is not particularly limited, but from the viewpoint of reactivity, selectivity, cost, etc., 1 ⁇ 10 -5 to 1 ⁇ 10 -1 mol per 1 mol of the above silane compound (VI) is used. Preferably, 1 ⁇ 10 -4 to 0.5 ⁇ 10 -1 mol is more preferable.
  • a solvent can also be used.
  • the solvent examples include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like.
  • Ester-based solvents; aprotonic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon-based solvents such as dichloromethane and chloroform. These solvents may be used alone or in admixture of two or more.
  • the reaction temperature in the hydrosilylation reaction is not particularly limited, and can usually be carried out at a temperature of 0 ° C. or higher, and if necessary, under heating conditions, but 0 to 200 ° C. is preferable. In order to obtain an appropriate reaction rate, the reaction is preferably carried out under heating, and from such a viewpoint, the reaction temperature is more preferably 40 to 110 ° C, further preferably 40 to 90 ° C.
  • the reaction time is also not particularly limited, and is usually about 1 to 60 hours, but 1 to 30 hours is preferable, and 1 to 20 hours is more preferable.
  • the functional group-modified conjugated diene polymer (F) one functional group having a partial structure represented by the above formula (V) or the above formula (VII) may be contained alone, or two or more thereof are contained. You may. Therefore, the functional group-modified conjugated diene-based polymer (F) may be a diene-based polymer modified with one compound selected from the group consisting of the above-mentioned silane compound (IV) and silane compound (VI). Alternatively, it may be a diene-based polymer modified with two or more kinds of compounds.
  • Z in the above formula (II) is preferably Si, Sn, B, and is preferably Si. More preferably.
  • the functional group V in the above formula (II) is an alkoxy.
  • the group is preferable, the alkoxy group having 1 to 5 carbon atoms is more preferable, and the methoxy group and the ethoxy group are particularly preferable.
  • n in the above formula (II) is an integer satisfying the above formula (5), it binds to the reactivity in the coupling step described later and the branch point of the obtained hydrogenated conjugated diene-based graft polymer (G). From the viewpoint of controlling the number of side chains, 2 or more is preferable, 3 or more is more preferable, and it is particularly preferable that it is the same as “Z valence-1”.
  • the average number of portions represented by the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F) is preferably 1 to 50, more preferably 2 to 30, and further 3 to 20. preferable.
  • the average number of functional groups V in the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F) is preferably 2 to 150, more preferably 4 to 90, and 6 to 60. More preferred.
  • the average number of functional groups V in the above formula (II) per molecule of the functional group-modified conjugated diene-based polymer (F) is the functional group of the functional group V contained in the functional group-modified conjugated diene-based polymer (F). It is calculated from the following formula (9) using the equivalent (g / eq) and the number average molecular weight (Mn) converted to standard polystyrene.
  • the functional group equivalent of the functional group V contained in the functional group-modified conjugated diene polymer (F) is the amount of the conjugated diene per functional group V and other monomers other than the conjugated diene contained as necessary. Means mass.
  • the functional group equivalent is calculated from the area ratio of the peak derived from the functional group V to the peak derived from the polymer main chain using 1 H-NMR.
  • the peak derived from the functional group V refers to the peak derived from the alkoxy group and the hydroxyl group.
  • the mixing ratio of the unmodified conjugated diene polymer (F') and the above-mentioned silane compound (IV) or silane compound (VI) is, for example, the formula (II) per molecule of the functional group-modified conjugated diene polymer (F).
  • the average number of functional groups V contained in) may be appropriately set to a desired value.
  • the unmodified conjugated diene polymer (F') and the above-mentioned silane compound (IV) or silane compound (VI) may be set.
  • the preferred range of Mw and vinyl content 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 0.1 to 2,000 Pa ⁇ s, more preferably 0.1 to 1500 Pa ⁇ s, and 0.1 to 1000 Pa ⁇ s. -S is more preferable.
  • the melt viscosity of the functional group-modified conjugated diene polymer (F) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good.
  • the active terminal polymer (I) is reacted with the functional group-modified conjugated diene polymer (F) to cause the functional group V in the portion represented by the above formula (II) and the above.
  • the substitution reaction of the active terminal polymer (I) occurs, and a conjugated diene-based graft polymer (G') in which the active terminal polymer (I) as a side chain is bonded to the heteroatom Z which is a branch point is formed. (Hereinafter, this reaction is referred to as a coupling reaction).
  • the functional group V (at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group) that has not reacted in the coupling reaction and the inactivation step described later remains as it is or is hydrolyzed.
  • at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group bonded to the branch point of the hydrogenated conjugated diene graft polymer (G) is formed.
  • the molar ratio of (amount of active terminal polymer (I) charged) / (amount of functional group-modified conjugated diene polymer (F) charged) is as described above per molecule of hydrogenated conjugated diene graft polymer (G).
  • the average number W of the side chains (b) directly bonded to the branch point may be appropriately set to a desired value, but is preferably 1 to 200, more preferably 2 to 100, for example. It is more preferably 3 to 50. If the molar ratio of (amount of active terminal polymer (I) charged) / (amount of functional group-modified conjugated diene polymer (F) charged) is less than 1, the number of side chains that can be introduced decreases, and is greater than 200. If it is large, the coupling rate described later tends to decrease.
  • the coupling reaction is usually carried out in a temperature range of 0 to 100 ° C. for 0.5 to 50 hours.
  • the functional group-modified conjugated diene polymer (F) may be diluted and used, and the diluting solvent is not particularly limited as long as it is inactive with respect to the active terminal and does not adversely affect the reaction.
  • the diluting solvent is not particularly limited as long as it is inactive with respect to the active terminal and does not adversely affect the reaction.
  • hexane or cyclohexane Saturated aliphatic hydrocarbons such as heptane, octane, decane, toluene, benzene and xylene, or aromatic hydrocarbons.
  • a Lewis base may be added as an additive during the coupling reaction.
  • Lewis base examples include 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 and N-methylmorpholine. And the like, amines and the like. These Lewis bases may be used alone or in combination of two or more.
  • the functional group-modified conjugated diene polymer (F) may be added to the reaction vessel in which the active terminal polymer (I) is synthesized, or conversely, the functional group-modified conjugated diene system may be added.
  • the active terminal polymer (I) may be added to the polymer (F).
  • both the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) may be diluted with a solvent and used if necessary.
  • the active terminal polymer (I) may be used alone or in combination of two or more, and the functional group-modified conjugated diene polymer (F) may also be used alone. Also, two or more types may be used in combination.
  • the coupling rate in the coupling reaction is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. If the coupling ratio is less than 50%, the mechanical properties of the obtained hydrogenated conjugated diene-based graft polymer (G) are deteriorated, which is not preferable.
  • the coupling rate is increased by increasing the amount of the functional group-modified conjugated diene polymer (F) added, increasing the amount of Lewis base added, increasing the reaction temperature, or increasing the reaction time. be able to.
  • the coupling reaction can be carried out until the coupling rate reaches a desired range. After that, the coupling reaction can be stopped by adding a polymerization terminator such as methanol or isopropanol.
  • the number of functional groups (c) directly bonded to the branch point is determined by the molar ratio of the amount of the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) charged in the coupling reaction, and the molar ratio of the amount charged.
  • the number of functional groups (c) directly bonded to the branch point to a desired range
  • the amount of the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) charged was carried out at a molar ratio such that the average number (X / Y) of the functional groups (c) per branch point contained in the hydrogenated conjugated diene-based graft polymer (G) was 1 or more.
  • Examples thereof include a method of inactivating a part of the remaining functional group (unreacted functional group V) described above so that (X / Y) is less than 1.
  • Step (A-2) The method for producing a hydrogenated conjugated diene-based graft polymer (G) of the present invention is described in step (A-1) in order to adjust the number of functional groups (c) directly bonded to the branch point to a desired range.
  • (A-2) At least selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene-based graft polymer (G') or in a hydrogenated conjugated diene-based graft polymer (G) that has undergone a hydrogenation step described later.
  • a step of inactivating a part of one remaining functional group (functional group V existing unreacted) hereinafter referred to as an inactivating step); Is a preferred embodiment.
  • the inactivation step (A-2) is preferably performed before the recovery step (C) because it is considered that they are likely to cause a condensation reaction with each other. Further, the inactivation step (A-2) may be performed before or after the hydrogenation step (B), but the ease of adjusting the number of functional groups (c) and the hydrogenation step (B). From the viewpoint of reactivity, it is preferable to carry out before the hydrogenation step (B).
  • Examples of the reagent used for inactivating the alkoxy group and the hydroxyl group include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, and the like.
  • Alkyl lithiums such as sec-butyl lithium and t-butyl lithium; alkyl sodiums such as methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium and t-butyl sodium; methyl Alkyl potassiums such as potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, t-butyl potassium; methylmagnesium bromide, ethylmagnesium bromide, t-butylmagnesium bromide, t-butyl Alkyl magnesium halides such as magnesium chloride and sec-butylmagnesium iodide; dialkyl copper lithium such as dimethyl copper lithium, diethyl copper lithium, methyl ethyl copper lithium, methyl n-propyl copper lithium, ethyl n-butyl copper lithium
  • Luis bases such as lithium diisopropylamide, lithium diisoethylamide, lithium dit-butylamide and the like; Among these, n-butyllithium, sec-butyllithium, methyllithium, methylmagnesium bromide, and dimethylcopper lithium are preferable because it is desirable that the steric hindrance is small in order to allow the inactivation reaction to proceed rapidly.
  • the molar ratio of the total amount is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 2.0 or more. Further, it is preferably 100 or less, more preferably 50 or less, and further preferably 20 or less.
  • the inactivation reaction in the above step (A-2) is usually carried out in a temperature range of 0 to 100 ° C. for 0.1 to 50 hours.
  • the inactivating reagent may be diluted and used, and the diluting solvent is not particularly limited as long as it is inactive with respect to the inactivating reagent and does not adversely affect the reaction.
  • the diluting solvent is not particularly limited as long as it is inactive with respect to the inactivating reagent and does not adversely affect the reaction.
  • Saturated aliphatic hydrocarbons such as decane, toluene, benzene and xylene or aromatic hydrocarbons can be mentioned.
  • a Lewis base may be added as an additive during the inactivation reaction, and examples of the Lewis base include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. Examples thereof include amines such as triethylamine, N, N, N', N'-tetramethylethylenediamine and N-methylmorpholin. These Lewis bases may be used alone or in combination of two or more.
  • the inactivation reaction can be carried out until the number of functional groups (c) directly bonded to the branch point reaches a desired range. Then, the inactivating reagent can be inactivated by adding a polymerization terminator such as methanol or isopropanol.
  • a polymerization terminator such as methanol or isopropanol.
  • Step (B) The method for producing a hydrogenated conjugated diene-based graft polymer of the present invention is (B) A step of hydrogenating the conjugated diene-based graft polymer (G') to form a hydrogenated conjugated diene-based graft polymer (G); including.
  • the hydrogenated conjugated diene-based graft polymer of the present invention can be obtained.
  • the method of hydrogenation is not particularly limited, and for example, a known method can be used.
  • the above steps (A-1) (or step (A-2)) and hydrogenation may be continued, or the conjugated diene-based graft polymer may be isolated and then hydrogenated.
  • the method for isolating the conjugated diene-based graft polymer is the same as the recovery step (C) described later.
  • a catalyst capable of hydrogenating a carbon-carbon double bond contained in an olefin compound or the like can be used.
  • examples of such a catalyst usually include a heterogeneous catalyst, a homogeneous catalyst and the like.
  • the non-uniform catalyst is not particularly limited, and specific examples thereof 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, and palladium zeolite.
  • the homogeneous catalyst is not particularly limited, and specific examples thereof include a Ziegler-based catalyst composed of a transition metal compound and alkylaluminum or alkyllithium; a metallocene-based catalyst.
  • transition metal compounds used in Cheegler-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; titanosendichloride, zirconosen. Cobalt can be mentioned.
  • alkylaluminum used in the Ziegler-based catalyst include trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum.
  • alkyllithium used in the Ziegler-based catalyst include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium. These homogeneous catalysts may be used alone or in admixture of two or more. Further, the homogeneous catalyst may be used by mixing with the heterogeneous catalyst.
  • the reaction activity is generally lower than that of the low molecular weight compound. Therefore, relatively high temperature and high pressure conditions are often preferable as the reaction conditions, and it is preferable to use a heterogeneous catalyst having high thermal stability. From the viewpoint of hydrogenation activity, it is preferable to use nickel or palladium as the metal having hydrogenation activity. Further, in order to suppress an undesired side reaction during the hydrogenation reaction, it is preferable to use calcium carbonate or a carbon carrier as the carrier, and it is more preferable to use a carbon carrier.
  • the hydrogenation reaction is usually carried out in an organic solvent.
  • the organic solvent is not particularly limited, and for example, the solvent used in the anionic polymerization exemplified in the above step (A-1) can be used.
  • the conjugated diene-based graft polymer (G') is present in the solvent used in the step (A-1), and the organic solvent is not particularly treated. This may be carried out, a part of the solvent may be removed by a method such as distillation and then carried out in the remaining solvent, or the solvent may be separately diluted with an organic solvent and then carried out in the solvent.
  • the conjugated diene-based graft polymer (G') is once taken out, and the conjugated diene-based graft polymer (G') is placed in an organic solvent. And the hydrogenation reaction may be carried out in the solvent.
  • the amount of the organic solvent used is such that the concentration of the conjugated diene-based graft polymer (G') in the reaction solution is 1% by mass or more and 30% by mass or less. Is preferable. If it is less than 1% by mass, the productivity may be remarkably lowered, and if it is more than 30% by mass, the viscosity may be remarkably increased and the mixing efficiency may be lowered.
  • the reaction pressure of the hydrogenation reaction may be appropriately set according to the catalyst to be used, etc., but the total pressure is usually 0.1 MPa to 20 MPa, preferably 0.5 MPa to 15 MPa, and more preferably 0.5 MPa to 5 MPa. is there.
  • the hydrogenation reaction is carried out in the presence of hydrogen gas, but it may be carried out in the presence of a gas other than hydrogen gas mixed with a gas inactive in the hydrogenation reaction.
  • a gas other than hydrogen gas mixed with a gas inactive in the hydrogenation reaction.
  • Specific examples of the gas inert to the hydrogenation reaction include nitrogen, helium, argon, and carbon dioxide.
  • the solvent used in the reaction may have a partial pressure at a significant ratio as a gas component, but such a situation is usually not a problem as long as the hydrogenation reaction proceeds.
  • the reaction temperature of 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., and more preferably 70 ° C. to 180 ° C. In general, it may be desirable for a heterogeneous catalyst to react at a higher temperature than a homogeneous catalyst.
  • the reaction time of the hydrogenation reaction may be appropriately set according to the type of catalyst used, the amount of catalyst, and the reaction temperature, but 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, the progress of unwanted side reactions becomes remarkable, and the hydrogenated conjugated diene-based graft polymer (G) 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 and the like.
  • the reaction type include a batch reaction type, a semi-continuous reaction type (semi-batch reaction type), and a continuous reaction type.
  • Suitable continuous reaction types include a plug flow type (PFR), a continuous flow stirring type (CSTR), and the like.
  • PFR plug flow type
  • CSTR continuous flow stirring type
  • examples of the mixing method include a mixing method by stirring and a mixing method in which the reaction solution is circulated in a loop format.
  • the reaction is carried out by a suspension bed, resulting in a gas-liquid-solid reaction field.
  • a homogeneous catalyst When a homogeneous catalyst is used under mixed conditions, it becomes a gas-liquid two-phase reaction field.
  • the hydrogenation reaction in the reactor is once terminated, the reaction solution is withdrawn, and at least a part of the withdrawn reaction solution is put into the same or different reactors, and hydrogenation is carried out in a reaction form in which the hydrogenation reaction is further carried out.
  • the reaction may be carried out.
  • the hydrogenation reaction is carried out in such a reaction form, it is possible to avoid the localization of heat generation associated with the hydrogenation reaction, and the hydrogenation rate may be improved.
  • the hydrogenation reaction may be carried out by one kind of reaction form alone, or may be carried out by combining two or more reaction forms which are the same or different.
  • it may be desirable to use a fixed bed reaction vessel and perform a hydrogenation reaction step including a step of reacting in a plug-flow format.
  • the amount of the catalyst used in the hydrogenation reaction may be appropriately set according to the type of catalyst used, the concentration of the conjugated diene-based graft polymer (G'), the reaction type, etc.
  • the amount of the catalyst used per 100 parts by mass of the reaction solution containing the conjugated diene graft polymer (G') is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass. Parts, 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 concentration in the reaction solution containing the conjugated diene-based graft polymer (G') of the transition metal compound is usually 0.001 mmol / liter to 100 mmol /. It is liters, preferably 0.01 mmol / liter to 10 mmol / liter.
  • the catalyst used in the hydrogenation reaction may be separated from the liquid containing the hydrogenated conjugated diene-based graft polymer (G), if necessary, after the hydrogenation reaction is completed.
  • the method of separation is not particularly limited as long as the catalyst can be separated.
  • the catalyst can be separated by, for example, continuous or batch filtration, centrifugation, sedimentation by standing and decantation.
  • the catalyst can be separated by, for example, coagulation precipitation, adsorption, washing and aqueous phase extraction.
  • the catalyst after use is separated by these separation methods, a trace amount of metal component derived from the catalyst may remain in the liquid containing the hydrogenated conjugated diene-based graft polymer (G).
  • the remaining metal component can be separated by a separation method such as coagulation precipitation, adsorption, washing, and aqueous phase extraction as described above.
  • the catalyst recovered by separation can be used again in the hydrogenation reaction after removing a part thereof or adding a new catalyst, if necessary.
  • Step (C) The method for producing a hydrogenated conjugated diene-based graft polymer (G) of the present invention is as follows. (C) Step of recovering the obtained hydrogenated conjugated diene-based graft polymer (G); including.
  • step (C) the obtained hydrogenated conjugated diene-based graft polymer (G) of the present invention is recovered.
  • the method for recovering the hydrogenated conjugated diene-based graft polymer (G) is not particularly limited, but a solution containing the hydrogenated conjugated diene-based graft polymer (G) can be obtained in step (B) or step (A-2). If so, for example, the obtained solution is poured into a poor solvent such as methanol to precipitate a hydrogenated conjugated diene-based graft polymer (G), or the polymerization reaction solution is poured into hot water together with steam to form a solvent. Is removed by co-boiling (steam stripping) and then dried, or the polymerization reaction solution is washed with water, separated and dried to isolate the hydrogenated conjugated diene-based graft polymer (G). Can be recovered by.
  • a poor solvent such as methanol
  • the polymerization reaction solution is poured into hot water together with steam to
  • the polymer composition of the present invention contains the hydrogenated conjugated diene-based graft polymer (G) of the present invention. Further, the polymer composition may further contain a polymer ( ⁇ ) other than the hydrogenated conjugated diene-based graft polymer (G).
  • the other polymer ( ⁇ ) may be a thermoplastic polymer ( ⁇ 1) or a curable polymer ( ⁇ 2).
  • thermoplastic polymer ( ⁇ 1) examples include acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester polymers or copolymers; polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-. 1.
  • Olefin resins such as poly-4-methylpentene-1, polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, Sterite resins such as ACS resin and MBS resin; styrene-methyl methacrylate copolymer; styrene-methyl methacrylate-maleic anhydride copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; nylon 6, Polyamides such as nylon 66 and polyamide elastomers; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polyacetal; vinylidene fluoride; polyurethane; modified polyphenylene ether; polyphenylene sulfide; silicone
  • Examples of the curable polymer ( ⁇ 2) include epoxy resin, unsaturated polyester resin, epoxy (meth) acrylate resin, ester (meth) acrylate resin, phenol resin, urea resin, melamine resin, thermosetting urethane resin, and silicon.
  • Examples thereof include resins, imide resins, furan resins, alkido resins, allyl resins, and diallyl phthalate resins.
  • epoxy resins and unsaturated polyesters are made from the viewpoints of availability and basic physical properties of the cured product, as well as the ability to remove air bubbles and the toughness of the obtained cured product to obtain a more excellent polymer composition.
  • Resins and epoxy (meth) acrylate resins are preferable, and among them, epoxy resins and unsaturated polyester resins are more preferable, and epoxy resins are even more preferable.
  • the curable polymer ( ⁇ 2) may be used alone or in combination of two or more.
  • the polymer composition contains a hydrogenated conjugated diene-based graft polymer (G) and another polymer ( ⁇ )
  • the hydrogenated conjugated diene-based graft polymer (G) and another polymer ( ⁇ ) The mass ratio (G) / ( ⁇ ) with and from is preferably 1/99 to 99/1.
  • additives may be added to the polymer composition of the present invention to the extent that the effects of the present invention are not impaired.
  • the other polymer ( ⁇ ) is a thermoplastic polymer ( ⁇ 1)
  • such additives include, for example, a reinforcing agent or filler such as calcium carbonate, silica, carbon black, glass fiber, clay, and a process oil.
  • a reinforcing agent or filler such as calcium carbonate, silica, carbon black, glass fiber, clay, and a process oil.
  • Polyethylene glycol, glycerin, phthalates and other plasticizers can be used as additives.
  • examples of other additives include heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, lubricants, and surfactants.
  • a foaming agent can be mentioned as the additive, and a foam can be prepared from a polymer composition containing the foaming agent and the thermoplastic polymer ( ⁇ 1).
  • the additive may be a curing agent, a curing accelerator, a known rubber, a thermoplastic elastomer, a core-shell particle, or the like.
  • examples include agents, fillers (inorganic particles such as silica, talc, calcium carbonate, aluminum hydroxide, etc.), flame retardants, defoaming agents, pigments, dyes, antioxidants, weather resistant agents, lubricants, mold release agents, and the like.
  • the polymer composition of the present invention can be prepared by a usual mixing method of polymer substances according to the composition ratio of each component such as a hydrogenated conjugated diene-based graft polymer (G) and another polymer ( ⁇ ). ..
  • a polymer composition can be prepared by, for example, a mixing device such as an extruder, a mixing roll, a Banbury mixer, or a kneader.
  • a method of melt-kneading using these mixing devices is a preferable aspect.
  • the other polymer ( ⁇ ) is a curable polymer ( ⁇ 2)
  • the polymer composition is sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, and then cooled and pulverized to prepare the polymer composition. Can be made.
  • the polymer composition of the present invention can be made into a molded product by various conventionally known molding methods.
  • the other polymer ( ⁇ ) is a thermoplastic polymer ( ⁇ 1)
  • the polymer composition is molded by, for example, extrusion molding, injection molding, hollow molding, compression molding, vacuum molding, calendar molding, or the like.
  • a product can be manufactured.
  • molded products, sheets, films and the like having various shapes can be obtained.
  • a molded product in the form of a non-woven fabric or a fibrous material can be produced by a method such as a melt blow method or a spunbond method.
  • the other polymer ( ⁇ ) is a curable polymer ( ⁇ 2)
  • a molded product obtained by heat-curing the polymer composition for example, by a transfer molding method can be produced.
  • Other molding methods when the polymer composition contains the curable polymer ( ⁇ 2) include, for example, an injection molding method and a compression molding method.
  • the molded product obtained from the polymer composition is used, for example, for interior / exterior parts for automobiles such as bumpers and instrument panels, televisions, stereos, and cleaning.
  • Housing materials for home appliances such as machines, electrical and electronic parts such as connectors, materials for electric wires and cables, trays for meat and fresh fish, fruit and vegetable packs, food packaging materials such as frozen food containers, packaging materials for food containers, industrial materials, sports Sporting goods such as shoe materials, fabric or leather products, toys, daily miscellaneous goods such as sandals, various films, sheets, laminated materials for molded products, adhesives / adhesives, elastic materials used for paper diapers, hoses, tubes, belts Various rubber products such as, medical supplies, etc. can be mentioned.
  • the other polymer ( ⁇ ) is a curable polymer ( ⁇ 2)
  • the use of the polymer composition, the cured product thereof, or the molded product is, for example, an adhesive for a fiber reinforcing composite material (fiber reinforcing composite material for concrete).
  • Various adhesives such as (adhesives for assembling parts in transportation equipment, etc.); various paints such as anticorrosion / waterproof paint for water and sewage, anticorrosion paint for metal;
  • Various coating primers such as coating primers; various lining materials such as metal lining materials, concrete lining materials, tank lining materials; various repair materials such as crack repair materials for concrete; printed wiring boards, insulating boards, semiconductor seals Examples include various electrical and electronic parts such as stopping materials and packaging materials.
  • 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 hydrogenated conjugated diene-based graft polymer and the polymer at each stage of its production. ) was calculated in terms of standard polystyrene.
  • the content was calculated, and the content of the structural unit derived from styrene was calculated from the area ratio of the peak of the aromatic ring derived from the structural unit derived from styrene and the peak of the double bond derived from the structural unit derived from the conjugated diene. ..
  • the vinyl content and the structural unit content derived from styrene were determined by 1 H-NMR of the conjugated diene-based graft polymer before hydrogenation.
  • the hydrogenation rate is calculated from the ratio of the peaks of double bonds derived from structural units derived from the conjugated diene of the conjugated diene-based graft polymer before hydrogenation and the hydrogenated conjugated diene-based graft polymer after hydrogenation. did.
  • Equipment Nuclear magnetic resonance equipment "JNM-ECX400" manufactured by JEOL Ltd.
  • Solvent Deuterated chloroform Measurement temperature: 50 ° C Accumulation number: 1024 times
  • the average number (X / Y) of functional groups (c) (at least one selected from the group consisting of alkoxy groups and hydroxyl groups) per Si atom (branch point) contained in the hydrogenated conjugated diene-based graft polymer is water. It is obtained from the results of measuring 29 Si-NMR of a conjugated diene-based graft polymer. Specifically, the integral value of Si with one functional group (c) bonded, Si with two functional groups (c) bonded, etc. multiplied by the number of functional groups is summed and integrated.
  • Average number of functional groups (c) per molecule of hydrogenated conjugated diene-based graft polymer is the average number of functional groups (c) per Si atom (branch point) contained in the hydrogenated conjugated diene-based graft polymer. It was calculated from the following formula using (X / Y) and the average number Y of Si atoms per molecule of the hydrogenated conjugated diene-based graft polymer.
  • Average number of side chains (b) per molecule of hydrogenated conjugated diene-based graft polymer W The average number W of side chains (b) per molecule of the hydrogenated conjugated diene-based graft polymer is the activity that is a component of the side chains (b) of the hydrogenated conjugated diene-based graft polymer in the above-mentioned coupling step.
  • the charge amount (number of moles) of the terminal polymer (I) per active terminal and the charge amount (number of moles) of the functional group-modified conjugated diene polymer (F) were calculated from the following formula.
  • (Average number W of side chains (b) per molecule of hydrogenated conjugated diene-based graft polymer) (Amount of active terminal polymer (I) charged per active end, which is a component of side chain (b)) ( Number of moles)) / (Amount of charged functional group-modified conjugated diene polymer (F) (number of moles))
  • Average number of side chains (b) per Si atom (branch point) contained in the hydrogenated conjugated diene-based graft polymer (W / Y)
  • the average number (W / Y) of side chains (b) per Si atom (branch point) contained in the hydrogenated conjugated diene graft polymer is the side chain per molecule of the hydrogenated conjugated diene graft polymer (W / Y). It was calculated from the following formula using the average number W of b) and the average number Y of Si atoms per molecule of the hydrogenated conjugated diene-based graft polymer.
  • Chlorine content The chlorine content in the hydrogenated conjugated diene-based graft polymer was calculated by automatic combustion ion chromatography.
  • ⁇ Combustion device> ⁇ Equipment: Automatic sample combustion equipment "AQF-2100H” manufactured by Mitsubishi Chemical Analytech Co., Ltd. ⁇ Combustion temperature: 1000 °C -Absorbent: Ion-exchanged water ⁇ Ion chromatography> -Device: Thermo Fisher Scientific Ion Chromatograph "ICS-2100" -Separation column: "IonPac AS20" manufactured by Thermo Fisher Scientific -Eluent: KOH aqueous solution-Column temperature: 40 ° C
  • the transparency of the hydrogenated conjugated diene-based graft polymer was evaluated by the degree of haze (HAZE).
  • a hydrogenated conjugated diene-based graft polymer is dissolved in cyclohexane so that the concentration of the polymer is 30% by mass, and a spectroscopic haze meter "SH7000" manufactured by Nippon Denshoku Kogyo Co., Ltd. is used using a liquid cell having an optical path length of 10 mm.
  • the degree of cloudiness (HAZE) was measured using, and the transparency was evaluated by the following indexes.
  • Example 1 (Step (1)) A fully dried 5 L autoclave is replaced with nitrogen, 1370 g of cyclohexane and 240 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. 1250 g of butadiene was sequentially added and polymerized for 1 hour. Then, 14 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 460 g of the unmodified conjugated diene polymer (F'-1) obtained in the step (1) was charged in an autoclave having a capacity of 1 L, and nitrogen degassed while stirring at 60 ° C. for 3 hours. 0.6 g of t-butylperoxypivalate and 290 g of 3-mercaptopropyltriethoxysilane were added and reacted at 80 ° C. for 8 hours to obtain a functional group-modified conjugated diene polymer (F-1).
  • the obtained functional group-modified conjugated diene polymer (F-1) revealed the weight average molecular weight, vinyl content, and styrene of the main chain (a) of the hydrogenated conjugated diene graft polymer (G-1) described later.
  • the content of structural units derived from can be determined.
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-1) is 6,000, the vinyl content is 10 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number Y of Si atoms was eight.
  • Step (3) A fully dried 5 L autoclave was replaced with nitrogen, 2270 g of cyclohexane and 8.7 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was set to 50 ° C. under stirring conditions. While controlling the above, 570 g of isoprene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-1).
  • the polymer solution in the step (3) By sampling and analyzing the polymer solution in the step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-1) described later.
  • the structural unit content can be determined.
  • the weight average molecular weight of the obtained active terminal polymer (I-1) was 60,000, the vinyl content was 10 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-1) obtained in step (2) were added to the solution containing the active terminal polymer (I-1) obtained in step (3). 20 g of the diluted solution was added and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 26 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups. Then, 1.0 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-1) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-1), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-1).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-1) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum dried at 70 ° C. for 24 hours to hydrogenate.
  • the conjugated diene-based graft polymer (G-1) was recovered.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-1) is 486,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of Si atoms (branch points) per polymer molecule is 8, and average number of functional groups (c) per polymer molecule is 0.8.
  • the average number of functional groups (c) per Si atom (branch point) is 0.1, the average number of side chains (b) per polymer molecule is 8, and the average number of side chains per Si atom (branch point) is 8.
  • the average number of (b) was one.
  • Table 1 shows the types and amounts of each reagent used in Example 1
  • Table 3 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-1).
  • Examples 2 to 15 Hydrogenated conjugated diene graft polymer by the same method as in Example 1 except that the type and amount of each reagent used in steps (1) to (6) were changed as shown in Tables 1 and 2. (G-2) to (G-15) were obtained. The molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymers (G-2) to (G-15) are shown in Tables 3 and 4.
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1370 g of cyclohexane and 240 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. 1250 g of butadiene was sequentially added and polymerized for 1 hour. Then, 14 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 530 g of the unmodified conjugated diene polymer (F'-16) obtained in the step (1), 1400 g of toluene, were placed in a 5 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (1.8 ⁇ 10 -4 mol as platinum atom) and 1.1 g of acetic acid were charged. To this, 220 g of triethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C.
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-16) is 6,000, the vinyl content is 10 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number of Si atoms in was eight. 1750 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-16) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-16) used in the coupling reaction described later is used. ) was obtained.
  • Step (3) A fully dried 5 L autoclave was replaced with nitrogen, 2270 g of cyclohexane and 8.7 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was set to 50 ° C. under stirring conditions. 570 g of isoprene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-16). By sampling and analyzing the polymer solution in step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-16) described later. The structural unit content can be determined. The weight average molecular weight of the obtained active terminal polymer (I-16) was 60,000, the vinyl content was 10 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-16) obtained in step (2) were added to the solution containing the active terminal polymer (I-16) obtained in step (3). 20 g of the diluted solution was added and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 26 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups. Then, 1.0 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-16) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-16), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-16).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-16) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum dried at 70 ° C. for 24 hours to hydrogenate.
  • the conjugated diene-based graft polymer (G-16) was recovered.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-16) is 486,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of Si atoms (branch points) per polymer molecule is 8, and average number of functional groups (c) per polymer molecule is 0.8.
  • the average number of functional groups (c) per Si atom (branch point) is 0.1, the average number of side chains (b) per polymer molecule is 8, and the average number of side chains per Si atom (branch point) is 8.
  • the average number of (b) was one.
  • Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-16).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1580 g of cyclohexane and 56 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. While controlling in this manner, 11 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 700 g of the unmodified conjugated diene polymer (F'-17) obtained in the step (1) and 1400 g of toluene were placed in a 5 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (2.1 ⁇ 10 -5 mol as platinum atom) and 0.12 g of acetic acid were charged. To this, 34 g of triethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C.
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-17) is 26,000, the vinyl content is 50 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number of Si atoms in was four. 1710 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-17) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-17) used in the coupling reaction described later is used. ) was obtained.
  • Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. While controlling in this manner, 7.0 g of tetrahydrofuran and 340 g of butadiene were sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-17).
  • step (3) By sampling and analyzing the polymer solution in step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-17) described later.
  • the structural unit content can be determined.
  • the weight average molecular weight of the obtained active terminal polymer (I-17) was 5,000, the vinyl content was 50 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 1480 g of a diluted solution of the functional group-modified conjugated diene polymer (F-17) obtained in the step (2) was added to the solution containing the active terminal polymer (I-17) obtained in the step (3).
  • the coupling reaction was carried out at 50 ° C. for 2 hours.
  • 190 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups.
  • 21 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-17) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-17), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-17).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-17) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum dried at 70 ° C. for 24 hours to hydrogenate.
  • the conjugated diene-based graft polymer (G-17) was recovered.
  • the obtained hydrogenated conjugated diene-based graft polymer (G-17) has a weight average molecular weight of 46,000, Mw / Mn of 1.5, a structural unit content derived from styrene of 0% by mass, and a coupling rate of 0% by mass.
  • hydrogenation rate is 99 mol%
  • average number of Si atoms (branch points) per polymer molecule is 4, and average number of functional groups (c) per polymer molecule is 0.4.
  • the average number of functional groups (c) per Si atom (branch point) is 0.1
  • the average number of side chains (b) per polymer molecule is 4, and the side chains per Si atom (branch point).
  • the average number of (b) was one.
  • Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-17).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1580 g of cyclohexane and 56 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. While controlling in this manner, 11 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 700 g of the unmodified conjugated diene polymer (F'-18) and 1400 g of cyclohexane obtained in the step (1) were placed in a 5 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. It was charged and replaced with nitrogen. To this, 22 g of trimethyl borate and 1.8 g of triethylamine borane were added, and the reaction was carried out at 80 ° C. for 10 hours. After completion of the reaction, the mixture was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-18).
  • the obtained functional group-modified conjugated diene polymer (F-18) revealed the weight average molecular weight, vinyl content, and styrene of the main chain (a) of the hydrogenated conjugated diene graft polymer (G-18) described later.
  • the content of structural units derived from can be determined.
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-18) is 26,000, the vinyl content is 50 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number of B atoms in was four.
  • Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is set to 50 ° C. under stirring conditions. While controlling in this manner, 7.0 g of tetrahydrofuran and 340 g of butadiene were sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-18).
  • step (3) By sampling and analyzing the polymer solution in step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-18) described later.
  • the structural unit content can be determined.
  • the weight average molecular weight of the obtained active terminal polymer (I-18) was 5,000, the vinyl content was 50 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 1480 g of a diluted solution of the functional group-modified conjugated diene polymer (F-18) obtained in the step (2) was added to the solution containing the active terminal polymer (I-18) obtained in the step (3).
  • the coupling reaction was carried out at 50 ° C. for 2 hours.
  • 190 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups.
  • 21 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-18) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-18), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-18).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-18) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum dried at 70 ° C. for 24 hours to hydrogenate.
  • the conjugated diene-based graft polymer (G-18) was recovered.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-18) is 46,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of B atoms (branch points) per polymer molecule is 4, and average number of functional groups (c) per polymer molecule is 0.4.
  • the average number of functional groups (c) per B atom (branch point) is 0.1, the average number of side chains (b) per polymer molecule is 4, and the average number of side chains per B atom (branch point) is 4.
  • the average number of (b) was one.
  • Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-18).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1370 g of cyclohexane and 240 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. 1250 g of butadiene was sequentially added and polymerized for 1 hour. Then, 14 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 600 g of the unmodified conjugated diene polymer (F'-19) obtained in the step (1), 1400 g of cyclohexane, were placed in a 5 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 5.6 mL of a 2% by mass xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ("PC072" manufactured by Polymer System) and 120 g of trimethylchlorosilane were charged, and these were charged overnight. Was stirred.
  • PC072 platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-19) is 6,000, the vinyl content is 10 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number of Si atoms in was eight. 1750 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-19) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-19) used in the coupling reaction described later is used. ) was obtained.
  • Step (3) A fully dried 5 L autoclave was replaced with nitrogen, 2270 g of cyclohexane and 8.7 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was set to 50 ° C. under stirring conditions. 570 g of isoprene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-19). By sampling and analyzing the polymer solution in the step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-19) described later. The structural unit content can be determined. The weight average molecular weight of the obtained active terminal polymer (I-19) was 60,000, the vinyl content was 10 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, in a solution containing the active terminal polymer (I-19) obtained in the step (3), 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-19) obtained in the step (2) were added. 20 g of the diluted solution was added and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 26 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups. Then, 1.0 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-19) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-19), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-19).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-19) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum dried at 70 ° C. for 24 hours to hydrogenate.
  • the conjugated diene-based graft polymer (G-19) was recovered.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-19) is 486,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of Si atoms (branch points) per polymer molecule is 8, average number of functional groups (c) per polymer molecule is 0, Si atoms
  • the average number of functional groups (c) per (branch point) is 0, the average number of side chains (b) per polymer molecule is 8, and the number of side chains (b) per Si atom (branch point) is 8. The average number was one.
  • Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-19).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1580 g of cyclohexane and 56 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. While controlling in this manner, 11 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 700 g of the unmodified conjugated diene polymer (F'-20) obtained in the step (1), 1400 g of cyclohexane, were placed in a 5 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 5.6 mL of a 2% by mass xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ("PC072" manufactured by Polymer System) and 120 g of trimethylchlorosilane were charged, and these were charged overnight. Was stirred.
  • PC072 platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-20) is 26,000, the vinyl content is 50 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number of Si atoms in was four. 1680 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-20) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-20) used in the coupling reaction described later is used. ) was obtained.
  • Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is set to 50 ° C. under stirring conditions. Then, 7.0 g of tetrahydrofuran and 340 g of butadiene were sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-20).
  • the polymer solution in the step (3) By sampling and analyzing the polymer solution in the step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-20) described later.
  • the structural unit content can be determined.
  • the weight average molecular weight of the obtained active terminal polymer (I-20) was 5,000, the vinyl content was 50 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 1480 g of a diluted solution of the functional group-modified conjugated diene polymer (F-20) obtained in the step (2) was added to the solution containing the active terminal polymer (I-20) obtained in the step (3).
  • the coupling reaction was carried out at 50 ° C. for 2 hours.
  • 190 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups.
  • 21 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-20) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-20), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-20).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-20) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum dried at 70 ° C. for 24 hours to hydrogenate.
  • the conjugated diene-based graft polymer (G-20) was recovered.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-20) is 46,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of Si atoms (branch points) per polymer molecule is 4, average number of functional groups (c) per polymer molecule is 0, Si atoms The average number of functional groups (c) per (branch point) is 0, the average number of side chains (b) per polymer molecule is 4, and the average number of side chains (b) per Si atom (branch point) is 0. The average number was one. Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-20).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1370 g of cyclohexane and 240 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. 1250 g of butadiene was sequentially added and polymerized for 1 hour. Then, 14 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 460 g of the unmodified conjugated diene polymer (F'-21) obtained in the step (1) was charged in an autoclave having a capacity of 1 L, and nitrogen degassed while stirring at 60 ° C. for 3 hours. 0.6 g of t-butylperoxypivalate and 290 g of 3-mercaptopropyltriethoxysilane were added and reacted at 80 ° C. for 8 hours to obtain a functional group-modified conjugated diene polymer (F-21).
  • the obtained functional group-modified conjugated diene polymer (F-21) revealed the weight average molecular weight, vinyl content, and styrene of the main chain (a) of the hydrogenated conjugated diene graft polymer (G-21) described later.
  • the content of structural units derived from can be determined.
  • the weight average molecular weight of the obtained functional group-modified conjugated diene polymer (F-21) is 6,000, the vinyl content is 10 mol%, the structural unit content derived from styrene is 0% by mass, and each polymer molecule.
  • the average number of Si atoms in was eight.
  • Step (3) A fully dried 5 L autoclave was replaced with nitrogen, 2270 g of cyclohexane and 8.7 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was set to 50 ° C. under stirring conditions. While controlling the above, 570 g of isoprene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-21).
  • the polymer solution in the step (3) By sampling and analyzing the polymer solution in the step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-21) described later.
  • the structural unit content can be determined.
  • the weight average molecular weight of the obtained active terminal polymer (I-21) was 60,000, the vinyl content was 10 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-21) obtained in step (2) were added to the solution containing the active terminal polymer (I-21) obtained in step (3). 20 g of the diluted solution was added and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 1.0 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-21) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-21), 100 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-21).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-21) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum-dried at 70 ° C. for 24 hours.
  • the diene-based graft polymer (G-21) was insolubilized, and the gel fraction was 80% by mass or more.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-21) is 486,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of Si atoms (branching points) per polymer molecule is 8, 16 functional groups (c) per polymer molecule, Si atoms
  • the average number of functional groups (c) per (branch point) is 2, the average number of side chains (b) per polymer molecule is 8, and the average number of side chains (b) per Si atom (branch point) is 8.
  • the average number was 1 (weight average molecular weight, Mw / Mn, vinyl content, styrene unit content, average number of Si atoms (branching points) per polymer molecule, functional groups per polymer molecule ( The average number of c) and the average number per Si atom (branch point) are measured by measuring the polymer obtained by drying the polymer solution obtained in step (4) or step (5) under normal temperature and pressure. It is the value that was calculated).
  • Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-21).
  • Step (1) A fully dried 5 L autoclave is replaced with nitrogen, 1580 g of cyclohexane and 56 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is 50 ° C. under stirring conditions. While controlling in this manner, 11 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water.
  • Step (2) Subsequently, 700 g of the unmodified conjugated diene polymer (F'-22) obtained in the step (1) was charged into an autoclave having a capacity of 1 L, and nitrogen degassed while stirring at 60 ° C. for 3 hours. 0.9 g of t-butylperoxypivalate and 51 g of 3-mercaptopropyltriethoxysilane were added and reacted at 80 ° C. for 8 hours to obtain a functional group-modified conjugated diene polymer (F-22).
  • the obtained functional group-modified conjugated diene polymer (F-22) revealed the weight average molecular weight, vinyl content, and styrene of the main chain (a) of the hydrogenated conjugated diene graft polymer (G-22) described later.
  • the unit content can be determined.
  • the obtained functional group-modified conjugated diene polymer (F-22) has a weight average molecular weight of 26,000, a vinyl content of 50 mol%, a styrene unit content of 0% by mass, and Si atoms per polymer molecule. The average number was four.
  • Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is set to 50 ° C. under stirring conditions. Then, 7.0 g of tetrahydrofuran and 340 g of butadiene were sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-22).
  • step (3) By sampling and analyzing the polymer solution in step (3), it is derived from the weight average molecular weight, vinyl content, and styrene of the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G-22) described later.
  • the structural unit content can be determined.
  • the weight average molecular weight of the obtained active terminal polymer (I-22) was 5,000, the vinyl content was 50 mol%, and the structural unit content derived from styrene was 0% by mass.
  • Step (4) Subsequently, 1480 g of a diluted solution of the functional group-modified conjugated diene polymer (F-22) obtained in the step (2) was added to the solution containing the active terminal polymer (I-22) obtained in the step (3). The coupling reaction was carried out at 50 ° C. for 2 hours. Then, 20 g of methanol was added to stop the polymerization reaction to obtain a solution containing a conjugated diene-based graft polymer (G'-22) before hydrogenation.
  • Step (5) To the obtained solution containing the conjugated diene-based graft polymer (G'-22), 20 mL of a Ziegler-National hydrogenation catalyst (0.095 mmol / L cyclohexane solution) formed of nickel octylate and trimethylaluminum was added, and hydrogen was added. The reaction was carried out at a pressure of 1 MPa and 80 ° C. for 5 hours to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-22).
  • a Ziegler-National hydrogenation catalyst 0.095 mmol / L cyclohexane solution formed of nickel octylate and trimethylaluminum
  • Step (6) The obtained solution containing the hydrogenated conjugated diene-based graft polymer (G-22) was washed with water to remove the catalyst, and the polymer solution after the washing was vacuum-dried at 70 ° C. for 24 hours.
  • the diene-based graft polymer (G-22) was insolubilized, and the gel fraction was 80% by mass or more.
  • the weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-22) is 46,000, Mw / Mn is 1.5, the structural unit content derived from styrene is 0% by mass, and the coupling rate is 95%, hydrogenation rate is 99 mol%, average number of Si atoms (branching points) per polymer molecule is 4, average number of functional groups (c) per polymer molecule is 8, Si atoms.
  • the average number of functional groups (c) per (branch point) is 2, the average number of side chains (b) per polymer molecule is 4, and the average number of side chains (b) per Si atom (branch point) is 2.
  • the average number was 1 (weight average molecular weight, Mw / Mn, vinyl content, styrene unit content, average number of Si atoms (branching points) per polymer molecule, functional groups per polymer molecule ( The average number of c) and the average number per Si atom (branch point) are measured by measuring the polymer obtained by drying the polymer solution obtained in step (4) or step (5) under normal temperature and pressure. It is the value that was calculated).
  • Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene-based graft polymer (G-22).
  • the hydrogenated conjugated diene-based graft polymers of Comparative Example 1 and Comparative Example 2 in which the average number (X / Y) of the functional groups (c) per Si atom (branch point) is 0 have condensation reactivity. Since it is low, it is inferior in affinity with polar materials. Further, the hydrogenation conjugate of Comparative Example 3 and Comparative Example 4 in which the average number (X / Y) of the functional groups (c) per Si atom (branch point) is in the range of more than 1 (1 ⁇ (X / Y)).
  • the diene-based graft polymer had a large proportion of insoluble matter in the step of drying the polymer solution, and it was difficult to take it out.
  • the hydrogenated conjugated diene-based graft polymer of the present invention has excellent affinity with polar materials and high stability, it is used for automobile interior / exterior parts, electrical / electronic parts, packaging materials, sporting goods, and daily use. It can be effectively used in a wide range of fields such as miscellaneous goods, laminating materials, elastic materials, various rubber products, medical supplies, various adhesives, and various coating primers.

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JPS62225513A (ja) * 1986-03-26 1987-10-03 Shin Etsu Chem Co Ltd ブロツク・グラフト共重合体及びその製造法
JPH0425511A (ja) * 1990-05-22 1992-01-29 Mitsubishi Petrochem Co Ltd グラフト共重合体の製造法
JP2002308932A (ja) * 2001-02-01 2002-10-23 Kuraray Co Ltd ブロック共重合体および熱可塑性樹脂組成物
WO2018034195A1 (ja) * 2016-08-19 2018-02-22 旭化成株式会社 変性共役ジエン系重合体及びそのゴム組成物、並びにタイヤ
WO2018043700A1 (ja) * 2016-09-02 2018-03-08 株式会社クラレ ゴム組成物

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Publication number Priority date Publication date Assignee Title
JPS62225513A (ja) * 1986-03-26 1987-10-03 Shin Etsu Chem Co Ltd ブロツク・グラフト共重合体及びその製造法
JPH0425511A (ja) * 1990-05-22 1992-01-29 Mitsubishi Petrochem Co Ltd グラフト共重合体の製造法
JP2002308932A (ja) * 2001-02-01 2002-10-23 Kuraray Co Ltd ブロック共重合体および熱可塑性樹脂組成物
WO2018034195A1 (ja) * 2016-08-19 2018-02-22 旭化成株式会社 変性共役ジエン系重合体及びそのゴム組成物、並びにタイヤ
WO2018043700A1 (ja) * 2016-09-02 2018-03-08 株式会社クラレ ゴム組成物

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JPWO2022065399A1 (enrdf_load_stackoverflow) * 2020-09-25 2022-03-31
WO2022065399A1 (ja) * 2020-09-25 2022-03-31 株式会社クラレ 樹脂組成物及び成形品
JP7462061B2 (ja) 2020-09-25 2024-04-04 株式会社クラレ 樹脂組成物及び成形品

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