WO2021054427A1

WO2021054427A1 - Conjugated diene graft polymer and method for producing same

Info

Publication number: WO2021054427A1
Application number: PCT/JP2020/035407
Authority: WO
Inventors: 慶和上野; 神原　浩; 敦稲富; 順矢高井; 昭明馬
Original assignee: 株式会社クラレ
Priority date: 2019-09-20
Filing date: 2020-09-18
Publication date: 2021-03-25
Also published as: TW202116837A; JP7240787B2; JPWO2021054427A1

Abstract

The present invention provides a conjugated diene graft polymer which exhibits high stability, while having excellent affinity for a polar material.　A conjugated diene graft polymer wherein side chains (b), each of which is composed of a polymer that contains at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit, are bonded to a main chain (a), which is composed of a polymer that contains a conjugated diene unit, respectively via one heteroatom which serves as a branch point, while having a valence of 3 or more. With respect to this conjugated diene graft polymer, the main chain (a) is bonded to the branch points directly or via a linking chain; the side chains (b) are bonded to the branch points directly; the heteroatom is at least one atom selected from the group consisting of Si, Sn, Ge, Pb, P, B and Al; at least one functional group (c), which is selected from the group consisting of an alkoxy group and a hydroxyl group, is directly bonded to at least one of the branch points; if N is the valence of the heteroatom, B is the average number of the side chains (b) directly bonded to one branch point and C is the average number of the functional groups (c) bonded to one branch point, N, B and C satisfy a specific relationship; and if X is the average number of the functional groups (c) directly bonded to the branch points per one molecule of the conjugated diene graft polymer and Y is the average number of branch points per one molecule of the conjugated diene graft polymer, X and Y satisfy the relational expression 0 < (X/Y) < 1.

Description

Conjugated diene-based graft polymer and its production method

The present invention relates to a conjugated diene-based graft polymer having excellent affinity with polar materials and high stability, and a method for producing the same.

Conventionally, it has been known that 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. For example, a method is known in which a conjugated diene-based graft polymer is formed by reacting polybutadiene grafted with a silyl chloride group by hydrosilylation with a living polymer having an active terminal of living anionic polymerization (see Non-Patent Document 1). ). Further, it is known that 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). ..

International Publication No. 2018/034195

However, since the 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, the affinity with a polar material such as glass or silica is improved. There was room for. 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 present invention has been made in view of the above circumstances, and provides a conjugated diene-based graft polymer having excellent affinity with polar materials and high stability, and a method for producing the conjugated diene-based graft polymer. The purpose is to provide.

As a result of diligent studies by the present inventors, at least one single amount selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit via a branch point in a main chain composed of a polymer containing a conjugated diene unit. A conjugated diene-based graft polymer in which a side chain composed of a polymer containing a body unit is bonded directly or through a connecting chain, and the number of at least one group selected from the group consisting of an alkoxy group and a hydroxyl group bonded to the branch point. We have found that the conjugated diene-based graft polymer in which the amount is within a certain range has excellent affinity with polar materials and high stability, and has completed the present invention.

That is, the present invention provides the following [1] to [11].
[1] In the main chain (a) composed of a polymer containing a conjugated diene unit,
A side chain (b) consisting of a polymer containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units via one heteroatom having a valence of 3 or more, which is a branching point. ) Is a conjugated diene-based graft polymer bonded to it.
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 functional groups (c) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer and the average number Y of branch points per molecule of the conjugated diene-based graft polymer are the following formula (2);
0 <(X / Y) <1 (2)
Satisfy the relationship,
Conjugated diene graft polymer.
[2] The average number X of the functional groups (c) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is the following formula (3);
0 <X ≦ 10 (3)
The conjugated diene-based graft polymer according to [1], which satisfies the above relationship.
[3] The conjugated diene-based graft polymer according to [1] or [2], wherein the heteroatom is Si.
[4] The average number W of side chains (b) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer and the average number Y of branch points per molecule of the conjugated diene-based graft polymer are expressed by the following formulas (4). 4);
0.5 ≤ (W / Y) (4)
The conjugated diene-based graft polymer according to any one of [1] to [3], which satisfies the above relationship.

[5] (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).
(In formula (I), P represents a polymer chain containing at least one monomeric unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and 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

(In formula (II), V represents an alkoxy group or a hydroxyl group, Z is Si, Sn, Ge, Pb, P, B, or Al, and 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), and 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. ); And (B) Step of recovering the obtained conjugated diene-based graft polymer;
The method for producing a conjugated diene-based graft polymer according to [1], which comprises.
[6] Further, before the step (B),
(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;
The method for producing a conjugated diene-based graft polymer according to [5], which comprises.
[7] The method for producing a conjugated diene-based graft polymer according to [5] or [6], wherein Z in the formula (II) is Si.
[8] The method for producing a conjugated diene-based graft polymer according to any one of [5] to [7], wherein the functional group V in the formula (II) is an alkoxy group.
[9] The conjugated diene-based graft polymer according to any one of [1] to [4], which is obtained by the production method according to any one of [5] to [8].
[10] A polymer composition containing the conjugated diene-based graft polymer according to any one of [1] to [4] and [9].
[11] A molded product obtained by molding the polymer composition according to [10].

According to the present invention, a conjugated diene-based graft polymer having excellent affinity with a polar material and having high stability, and a method for producing the same are provided.

Hereinafter, the present invention will be described in detail.
The conjugated diene-based graft polymer of the present invention is
In the main chain (a) composed of a polymer containing a conjugated diene unit,
A side chain (b) consisting of a polymer containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units via one heteroatom having a valence of 3 or more, which is a branching point. ) Is a conjugated diene-based graft polymer bonded to it.
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 functional groups (c) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer and the average number Y of branch points per molecule of the conjugated diene-based graft polymer are the following formula (2);
0 <(X / Y) <1 (2)
Satisfy the relationship.
In the present invention, 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 body unit and the monomer unit constituting the polymer chain to be the side chain may be the same or different.

<Main chain (a)>
The conjugated diene-based graft polymer of the present invention has a main chain (a) composed of a polymer containing a conjugated diene unit. The main chain contained in the conjugated diene-based graft polymer of the present invention refers to the entire portion derived from all the monomer units including the conjugated diene unit constituting the main chain. For example, when a conjugated diene-based graft polymer is produced by the production method of the present invention, an unmodified conjugated diene-based polymer which is a precursor of the functional group-modified conjugated diene-based polymer (F) used in the production thereof. Refers to the entire part derived from (F'). For example, when the unmodified conjugated diene-based polymer (F') contains a vinyl-bonded butadiene unit, it is bonded to a carbon atom in _{the polymer skeleton (-(CC) n-)-CH =} It is called the main chain including the CH ₂ _{portion (the portion that becomes -CH-CH 2} -when a modifying compound is added).

The main chain (a) is derived from a unit other than a vinyl monomer unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, a residue of a coupling agent) in the polymer chain skeleton. It is preferable not to contain a unit having a Si atom or an N atom). When a unit other than the vinyl monomer unit is contained in the main chain skeleton, the main chain skeleton is cleaved under conditions where the bond between the hetero atom and carbon, which is a branching point described later, is broken, or by shearing or heat. Therefore, the physical properties tend to deteriorate. The polymer chain terminal, which is the main chain, may have a group other than the monomer unit.

The main chain (a) contains a conjugated diene unit as a monomer unit constituting the polymer. Examples of 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-octadien. , 1,3-Cyclohexadiene, 2-methyl-1,3-octadene, 1,3,7-octatriene, myrsen, farnesene, and conjugated diene other than butadiene and isoprene such as chloroprene. Among these conjugated diene, butadiene and isoprene are preferable, and butadiene is more preferable. The conjugated diene as the conjugated diene unit may be used alone or in combination of two or more.

In one embodiment, the main chain (a) is preferably at least one monomer unit selected from the group consisting of butadiene and isoprene in an amount of 50% by mass or more of all the monomer units constituting the polymer. is there. The total content of the butadiene unit and the isoprene unit is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, based on all the monomer units of the main chain (a).

Examples of the monomer unit other than the butadiene unit and the isoprene unit that can be contained in the main chain (a) include the above-mentioned conjugated diene unit other than butadiene and isoprene, and an aromatic vinyl compound unit.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-. Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Examples thereof include vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferable. The aromatic vinyl compound which is the unit of the aromatic vinyl compound may be used alone or in combination of two or more.

The content of the monomer unit other than the butadiene unit and the isoprene unit in the main chain (a) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. .. For example, when the aromatic vinyl compound unit is not more than the above range, the processability of the obtained conjugated diene-based graft polymer tends to be improved. Further, when the conjugated diene-based graft polymer is produced by the production method of the present invention, the reactivity tends to be improved when the unmodified conjugated diene-based polymer (F') is modified with a functional group.

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. In the present invention, the Mw of the main chain (a) is, for example, a functional group-modified conjugated diene polymer which is a component of the main chain described later when a conjugated diene-based graft polymer is produced by the production method of the present invention. (F), or Mw of the unmodified conjugated diene polymer (F'). When the Mw of the main chain (a) is within the above range, the process passability during manufacturing tends to be excellent and the economic efficiency tends to be good. In the present invention, unless otherwise specified, 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. In the present invention, the "vinyl content" refers to 1,2-bonds, 3,4-bonds (in the case of other than farnesene), and 3,13- in a total of 100 mol% of conjugated diene units contained in the polymer. Conjugated diene units that are bonded by bonding (in the case of farnesene) (conjugated diene units that are bonded by other than 1,4-bonding (in the case of non-farnesene) and 1,13-bonding (in the case of farnesene)) Means total mol%. The vinyl content is derived from conjugated diene units that are 1,2-bonded, 3,4-bonded (for non-farnesene), and 3,13-bonded (for farnesene) using ^{1 H-NMR.} It is calculated from the area ratio of the peak derived from the conjugated diene unit that is bonded to the peak of 1,4-bond (in the case of other than farnesene) and 1,13- bond (in the case of farnesene).

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 conjugated diene-based graft polymer tends to have excellent fluidity and low temperature characteristics. Further, when it is 50 mol% or more, the reactivity of the obtained conjugated diene-based graft polymer tends to be excellent.

When the conjugated diene-based graft polymer is produced by the production method of the present invention, the vinyl content of the main chain (a) is, for example, an unmodified conjugated diene-based polymer that is a component of the main chain (a). The desired value can be obtained by controlling the type of solvent used in producing (F'), 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 butadiene units, isoprene units and butadiene units, vinyl content of conjugated diene units other than isoprene units, types of conjugated diene units, and monomers other than conjugated diene. Although it may vary depending on the content of the unit and the like, −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.

<Side chain (b)>
The conjugated diene-based graft polymer of the present invention has a side chain (b) composed of a polymer containing at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit.

The side chain (b) contains at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit as the monomer unit constituting the polymer.

The specific example of the conjugated diene that can form the monomer unit of the side chain (b) is the same as the specific example of the conjugated diene that constitutes the monomer unit of the main chain (a). Among the conjugated diene to be the conjugated diene unit contained in the side chain (b), butadiene and isoprene are preferable. The conjugated diene as the conjugated diene unit may be used alone or in combination of two or more.

The specific example of the aromatic vinyl compound that can form the monomer unit of the side chain (b) is the same as the specific example of the aromatic vinyl compound that can form the monomer unit of the main chain (a). Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferable. The aromatic vinyl compound which is the unit of the aromatic vinyl compound may be used alone or in combination of two or more.

The side chain (b) is selected from the group in which the skeleton of the polymer chain consists of a homopolymer consisting of only one conjugated diene unit or one aromatic vinyl compound unit, a conjugated diene unit and an aromatic vinyl compound unit2. A copolymer consisting of more than one kind of monomer unit, or one or more monomer units selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit, and a vinyl simple substance other than the conjugated diene and an aromatic vinyl compound. It may be a copolymer with a monomer unit of a metric. Further, the polymer constituting the side chain (b) may be one kind alone or two or more kinds having different structures.

The ratio of the conjugated diene units that can form the side chain (b) is not particularly limited and can be designed according to the purpose, but it is preferably 50% by mass or more, and 60% by mass or more. Is more preferable, and is particularly preferably 70% by mass or more, and may be 100% by mass. When the ratio of the conjugated diene unit is 50% by mass or more, the processability of the obtained conjugated diene-based graft polymer tends to be improved.

The ratio of the aromatic vinyl compound unit that can form the side chain (b) is not particularly limited and can be designed according to the purpose, but it is preferably 50% by mass or more, and 60% by mass or more. It is more preferable, and it is particularly preferable that it is 70% by mass or more, and it may be 100% by mass. When the ratio of the aromatic vinyl compound unit is 50% by mass or more, the mechanical properties of the obtained conjugated diene-based graft polymer tend to be improved.

The side chain (b) is derived from a unit other than a vinyl monomer unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound (for example, a residue of a coupling agent) in the polymer chain skeleton. It is preferable not to contain (a unit having a Si atom or an N atom). When a unit other than the vinyl monomer is contained in the polymer chain skeleton of the side chain (b), the bond between the hetero atom and carbon, which is a branching point described later, is broken, or shear or heat. Since the polymer chain skeleton of the side chain (b) is cleaved by this, the physical properties tend to deteriorate. The end of the polymer chain to be the side chain may have a group other than the monomer unit.

The weight average molecular weight (Mw) of the side chain (b) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 80,000 or less, and 3,000 or more and 50 or less. More preferably, it is 000 or less. In the present invention, the Mw of the side chain (b) is, for example, the active terminal polymer (I) which is a component of the side chain described later when a conjugated diene-based graft polymer is produced by the production method of the present invention. It is Mw. 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, 1} H of the active terminal polymer (I) which is a component of the side chain, which will be described later, when a conjugated diene-based graft polymer is produced by the production method of the present invention. -Calculated from the 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 conjugated diene-based graft polymer tends to have excellent fluidity and low temperature characteristics. Further, when it is 50 mol% or more, the reactivity of the obtained conjugated diene-based graft polymer tends to be excellent.

The vinyl content of the side chain (b) is, for example, the active terminal polymer (I) which is a component of the side chain (b) when the conjugated diene-based graft polymer 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 above, the polar compound used as necessary, the polymerization temperature, and the like.

The glass transition temperature (Tg) of the side chain (b) may vary depending on the vinyl content of the conjugated diene unit, the type of the conjugated diene unit, the content of units derived from a monomer other than the conjugated diene, etc., but is -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.

<Conjugated diene graft polymer>
In the conjugated diene-based graft polymer of the present invention, the side chain (b) is bonded to the main chain (a) via one heteroatom having a valence of 3 or more, which is the branch point. At least one of the above is a conjugated diene-based graft polymer to which at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group is bonded.

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, and the functional group (c) is directly bonded to the branch point. Here, the term "bonded directly to the branch point" means that the branch point is directly bonded to the portion derived from the monomer unit constituting the main chain. A branch point and a bond through a connecting chain means that one end of the connecting chain is bonded to a portion derived from a monomer unit constituting the main chain, and the branch point is directly bonded to the other end of the connecting chain. It means that you are doing it. For example, when a branch point is bonded to a 1,2-bonded butadiene unit, the case represented by the following formula (III-1) is a case where the branch point is directly bonded to the main chain, and the following formula ( The case shown in III-2) is the case where the main chain is connected to the branch point through the connecting chain.

In the above formulas (III-1) and (III-2), Z ⁰ is a heteroatom serving as a branch point, and R ^2a is a connecting chain. Although R ^2a is a divalent organic group, an alkylene group which may have a hetero atom is preferable.

When the branch portion from the main chain including the bond form between the main chain (a) and the branch point is represented by a chemical formula, the form in which the branch point is directly bonded to the main chain (a) as shown in the following formula (III-3). There is a branch portion including, and a branch portion including a form connected to the branch point through a connecting chain as shown in the following formula (III-4). Among these branching portions, a branching structure including a form in which the branch point is connected to the branch point through a connecting chain as shown in the formula (III-4) is desirable.

In the above formulas (III-3) and (III-4), 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), and R ^2b is connected. It is a chain.

In formulas (III-3) and (III-4), V represents an alkoxy group or a hydroxyl group, Z ¹ is Si, Sn, Ge, Pb, P, B, or Al, and R ^2b has a heteroatom. Indicates an alkylene group having 1 to 12 carbon atoms which may be used, R ³ indicates an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a hydrogen atom, and P indicates a conjugated diene unit and an aromatic group. A polymer chain containing at least one monomer unit selected from the group consisting of group vinyl compound units 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)
When m is 2 or more, P may be the same or different, when n is 2 or more, V may be the same or different, and when N-mn is 2 or more, R ³ may be the same. ^{It may be different, and Z 1} may be the same or different when a plurality of branch points are included in the main chain. However, the conjugated diene-based graft polymer of the present invention needs to contain V (functional group (c)) and P (side chain (b)) while satisfying the relationship of the above formula (2). Further, in the conjugated diene-based graft polymer of the present invention, the main chain 1 for it if there is one or more side chains with respect to this, (Z ¹ m is 0) Z ¹ in which the side chain is not bound Can be included, but Z ¹ is also 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 and Sn 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like. Among the functional groups (c), 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. Among these R ³ , 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.

As ^{the alkylene group having 1 to 12 carbon atoms having a hetero atom 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.

In the conjugated diene-based graft polymer 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 the side directly bonded to one branch point. When the average number of chains (b) 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. By satisfying this condition, the branch point is bonded to the main chain (a) directly or through the connecting chain, and the conjugated diene-based graft polymer of the present invention has at least the side chain (b) and the functional group (c). Will be included.
N-1 ≧ B + C, B> 0, C> 0 (1)

The conjugated diene-based graft polymer of the present invention has an average number X of functional groups (c) directly bonded to the above-mentioned branch point per molecule of the conjugated diene-based graft polymer and a branch point per molecule of the conjugated diene-based graft polymer. The average number Y of the above satisfies the relationship of the following equation (2).
0 <(X / Y) <1 (2)
When the above (X / Y) is 0, the conjugated diene-based graft polymer tends to be inferior in affinity with the polar material, and when the above (X / Y) is 1 or more, the conjugated diene-based graft polymer tends to be inferior. Tends to be less stable.

From the viewpoint of being more excellent in affinity and stability with polar materials, 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. In the present invention, (X / Y) (average number of functional groups (c) per branch point contained in the conjugated diene graft polymer) is, for example, when Z is Si, the conjugated diene graft. Obtained from the results of measuring ^{29 Si-NMR of the polymer.} Specifically, the integral value obtained by multiplying the integrated value of Si having one functional group (c) bonded and Si having two functional groups (c) bonded by the number of functional groups is added up and integrated. Calculated by comparing with a simple sum of values. When Z is a heteroatom other than Si, the average number of the heteroatoms per molecule of the conjugated diene-based graft polymer can be obtained in the same manner.

Further, the average number Y of branch points per molecule of the conjugated diene graft polymer is a specific hetero atom (Si, Sn) in the conjugated diene graft polymer measured by an inductively coupled plasma mass spectrometer (ICP-MS). , Ge, Pb, P, B, and Al) and the number average molecular weight (Mn) converted to standard polystyrene are used to obtain from the following formula (8).
(Average number of bifurcation points per molecule of conjugated diene graft polymer Y) = [(heteroatom content (mass%)) / 100] × [(number average molecular weight Mn) / (molecular weight in styrene unit) × ( Conjugated diene and, if necessary, average molecular weight of other monomeric units other than conjugated diene)] / (Atomic weight of heteroatom) (8)

In the conjugated diene-based graft polymer of the present invention, the average number X of functional groups (c) directly bonded to the above-mentioned branch point per molecule of the conjugated diene-based graft polymer satisfies the relationship of the following formula (3). preferable.
0 <X ≦ 10 (3)
The average number X of the functional groups (c) is calculated by the method described later. When the X is 0, the conjugated diene-based graft polymer tends to have inferior affinity with the polar material, and when the X exceeds 10, the stability of the conjugated diene-based graft polymer tends to decrease. ..

From the viewpoint of being more excellent in affinity and stability with polar materials, 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. In the present invention, the average number X of the functional groups (c) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is the functional group per branch point contained in the conjugated diene-based graft polymer. It is determined by using the average number (X / Y) of (c) and the average number Y of branching points per molecule of the conjugated diene-based graft polymer.

The number of side chains (b) and the number of functional groups (c) directly bonded to the branch point are determined by, for example, the steps described later when the conjugated diene-based graft polymer is produced by the production method of the present invention. From the molar ratio of the charged amount of the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) in (A-1), and the group consisting of alkoxy groups and hydroxyl groups in the step (A-2) described later. The amount and reaction time of the reagent used to inactivate some of the at least one remaining functional group selected (unreacted functional group V), and of the polar compounds used as needed. It can be adjusted to a desired range depending on the type and the amount of addition.

The stability of the conjugated diene-based graft polymer can be evaluated, for example, by the appearance change and the formation of insoluble matter (gelled product) when stored for a long period of time at normal temperature and pressure. It is also possible to evaluate the conjugated diene-based graft polymer under conditions that promote the condensation reaction of the alkoxysilyl group or silanol group by heating and reducing the pressure.

Affinity with polar materials can be determined by, for example, measuring the peel strength after applying a conjugated diene-based graft polymer or a conjugated diene-based graft polymer composition on a glass substrate and heating it for a certain period of time to cure it. It can be evaluated by conducting a grid test or the like. In addition, the reactivity and affinity with polar materials such as glass and silica can be evaluated by the condensation reactivity of the alkoxysilyl group or silanol group. When a solution containing a conjugated diene-based graft polymer is shaken under acidic or basic conditions, insoluble matter (gelled product) is generated when the condensation reactivity is high. The reactivity with the material can be evaluated.

In the conjugated diene-based graft polymer of the present invention, the average number of side chains (b) directly bonded to the above-mentioned branch point per molecule of the conjugated diene-based graft polymer is W, and the number of branches per molecule of the conjugated diene-based graft polymer is W. When the average number of points is Y, it is preferable that (W / Y) satisfies the relationship of the following equation (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)). In the present invention, the average number W of side chains (b) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is the case where the conjugated diene-based graft polymer is produced by the production method of the present invention. , The amount (number of moles) of the active terminal polymer (I) to be the side chain (b) of the conjugated diene-based graft polymer per active terminal and the weight of the functional group-modified conjugated diene system in the following step (A-1). It is calculated from the following formula (9) using the charge amount (number of moles) of the coalescence (F).
(Average number W of side chains (b) directly bonded to the above-mentioned branch point per molecule of conjugated diene-based graft polymer) = (Preparation per active end of active terminal polymer (I) having side chain (b)) Amount (number of moles)) / (Amount of functional group-modified conjugated diene polymer (F) charged (number of moles)) (9)

Further, the average number Y of branch points per molecule of the conjugated diene-based graft polymer is calculated by the method described above. If the above (W / Y) is less than 0.5, the fluidity of the conjugated diene-based graft polymer is lowered, and the balance between processability and mechanical properties tends to be poor.

_{The degree of branching of the conjugated diene-based graft polymer is the slope (α s} ) when the radius of gyration (R) is plotted in both logarithmic ratios with respect to the weight average molecular weight (Mw) of the conjugated diene-based graft polymer by the absolute method. , Or the intrinsic viscosity (η) of the conjugated diene-based graft polymer obtained by the absolute method can be determined from the slope (αη) when both logarithmic plots are made. The random coil chain of a normal linear polymer _{shows a value of about 0.6 to 0.8 for both α s} and α η, and if it is less than 0.6, the existence of a branched chain is suggested. _{The value of α s} or α η of the conjugated diene-based graft polymer of the present invention is preferably less than 0.6, more preferably 0.55 or less, and further preferably 0.50 or less. The log-log plot of the weight average molecular weight (Mw) and the radius of gyration (R) or the intrinsic viscosity (η) by the absolute method of the conjugated diene-based graft polymer can be obtained by, for example, the SEC-MALS-VISCO method. 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. By combining (MALS) and a viscosity detector (VISCO), the radius of gyration and intrinsic viscosity of each molecular weight of the polymer solution size-sorted by SEC can be calculated. _{When the value of α s} or α η of the conjugated diene-based graft polymer of the present invention is in the above range, the fluidity of the conjugated diene-based graft polymer is improved, and the balance between processability and mechanical properties tends to be excellent.

In the conjugated diene-based graft polymer of the present invention, the average number W of side chains (b) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is preferably 1 or more, and preferably 2 or more. More preferably, it is more preferably 3 or more. 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 conjugated diene-based graft polymer tends to decrease, and the balance between processability and mechanical properties tends to be poor.

When the conjugated diene-based graft polymer is produced by the production method of the present invention, the average number W of the side chains (b) is, for example, the active terminal polymer (I) in the step (A-1) described later. ) And the amount of the functional group-modified conjugated diene polymer (F) charged can be adjusted to a desired range. For example, when (amount of active terminal polymer (I) charged (number of moles)) / (amount of functional group-modified conjugated diene polymer (F) charged (number of moles)) = 4/1, the side chain (b) ) Has an average number of W of 4. However, the upper limit of W is the number of functional groups V per molecule of the functional group-modified conjugated diene polymer (F).

The combination of the polymer that becomes the main chain (a) and the polymer that becomes the side chain (b) contained in the conjugated diene-based graft polymer is not particularly limited and may be the same or different, and is designed according to the purpose. It is possible. The 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.
(I) 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).
(Ii) The type or combination of the monomer units of the polymer serving as the main chain (a) is different from the type or combination of the monomer units of the polymer serving as the side chain (b).
(Iii) When the main chain (a) and the side chain (b) each contain a plurality of monomer units of the same type, the monomer unit composition ratio of the polymer to be the main chain (a) is on the side. It is different from the monomer unit composition ratio of the polymer to be the chain (b).
(Iv) When the main chain (a) and the side chain (b) each contain a conjugated diene unit, the vinyl content of the conjugated diene unit of the polymer to be the main chain (a) is the same as that of the side chain (b). It differs from the vinyl content of the conjugated diene unit of the polymer.

The conjugated diene-based graft polymer of the present invention may be at least one monomer unit selected from the group consisting of butadiene and isoprene in an amount of 50% by mass or more among all the monomer units constituting the polymer. This is a preferred embodiment. The total content of the butadiene unit and the isoprene unit is more preferably 60 to 100% by mass and further preferably 70 to 100% by mass with respect to all the monomer units of the conjugated diene-based graft polymer.

The content of monomer units other than the butadiene unit and the isoprene unit in the conjugated diene-based graft polymer of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass. The following is more preferable. For example, when the aromatic vinyl compound unit is not more than the above range, the processability of the conjugated diene-based graft polymer of the present invention tends to be improved.

The weight average molecular weight (Mw) of the conjugated diene-based graft polymer of the present invention is preferably 5,000 or more and 1,000,000 or less, preferably 30,000 or more and 1,000,000 or less. More preferably, it is more than 100,000 and less than 1,000,000. When the Mw of the conjugated diene-based graft polymer 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 conjugated diene-based graft polymer tends to be improved.

The molecular weight distribution (Mw / Mn) of the conjugated diene-based graft polymer of the present invention is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, still more preferably 1.0 to 5.0. 1.0 to 2.0 is particularly preferable. When Mw / Mn is within the above range, the variation in viscosity of the conjugated diene-based graft polymer is small, which is more preferable. In the present invention, Mn means a number average molecular weight, and Mn is a standard polystyrene-equivalent number average molecular weight obtained from GPC measurement. The molecular weight distribution (Mw / Mn) means the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene obtained by GPC measurement.

The melt viscosity of the conjugated diene-based graft polymer of the present invention 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. More preferred. When the melt viscosity of the conjugated diene-based graft polymer is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good. In the present invention, the melt viscosity of the conjugated diene-based graft polymer is a value measured by a Brookfield viscometer at 38 ° C.

The vinyl content of the conjugated diene-based graft polymer of the present invention 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 conjugated diene-based graft polymer is preferably 0.5 mol% or more, more preferably 1 mol% or more.

The vinyl content of the conjugated diene-based graft polymer 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 conjugated diene-based graft polymer described later. Tends to be low, and the fluidity and low temperature characteristics of the conjugated diene-based graft polymer tend to be excellent. Further, when it is 50 mol% or more, the reactivity of the conjugated diene-based graft polymer tends to be excellent.

The glass transition temperature (Tg) of the conjugated diene-based graft polymer is derived from butadiene unit, isoprene unit and butadiene unit, vinyl content of conjugated diene unit other than isoprene unit, type of conjugated diene unit, and monomer other than conjugated diene. Although it may vary depending on the content of the unit to be used, 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 of the main chain to the side chain in the conjugated diene-based graft polymer of the present invention is preferably in the range of 10/90 to 90/10, more preferably in the range of 15/85 to 80/20, and 20/80 to 70. A range of / 30 is even more preferred. When the mass ratio of the main chain to the side chain is in the above range, the processability of the polymer composition containing the conjugated diene-based graft polymer tends to be improved.

The conjugated diene-based graft polymer of the present invention preferably has a catalyst residue amount derived from the polymerization catalyst used for its production in the range of 0 to 200 ppm in terms of metal. For example, when 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, the metal that serves as a reference for the amount of catalyst residue is an alkali such as lithium. Become metal. When the amount of the catalyst residue is in the above range, the tack does not decrease during processing and the like, and the heat resistance of the conjugated diene-based graft polymer of the present invention is improved. The amount of catalyst residue derived from the polymerization catalyst used in the production of the conjugated diene-based graft polymer is more preferably 0 to 150 ppm, still more preferably 0 to 100 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.

Examples of the method for setting the amount of the catalyst residue of the conjugated diene-based graft polymer to such a specific amount include a method of purifying the conjugated diene-based graft polymer and sufficiently removing the catalyst residue. As a method for purification, washing with water or warm water, an organic solvent typified by methanol, acetone, or supercritical fluid carbon dioxide is preferable. From an economical point of view, 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. In addition, 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 conjugated diene-based graft polymer of the present invention preferably has a halogen content of 0 to 1,000 ppm. For example, when a silyl chloride-modified conjugated diene-based polymer is used as the functional group-modified conjugated diene-based polymer (F) for producing a conjugated diene-based graft polymer, the reference halogen is chlorine. When the halogen content is in the above range, transparency, heat resistance, and weather resistance tend to be good. The halogen content of the conjugated diene-based graft polymer 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.

As a method for setting the halogen content of the conjugated diene-based graft polymer to such a specific amount, a functional group-modified conjugated diene-based polymer (F), which is a raw material for producing the conjugated diene-based graft polymer, is used. As a by-product, a method using an alkoxysilane-modified conjugated diene-based polymer that does not produce a halide can be mentioned.

<Manufacturing method of conjugated diene-based graft polymer>
The method for producing the conjugated diene-based graft polymer of the present invention is not particularly limited, and for example, a macromonomer (a compound having a polymerizable functional group at the active end of a polymer obtained by polymerizing a monomer as a constituent unit of a side chain). A method of polymerizing a macromonomer obtained by reacting) with a monomer that is a constituent unit of the main chain, and reacting a polymer that constitutes the main chain synthesized in advance in the presence of tetramethylethylenediamine with an organic alkali metal compound. A method of polymerizing a monomer that is a constituent unit of a side chain after the main chain is lithiated by allowing the polymer to form a polymer having two active terminals that are constituents of the main chain and a polymer that is a constituent of the side chain. A method of preparing a mixture of polymers having two active terminals, adding a coupling agent having three or more reactive sites to the mixture and reacting the mixture, and using a functional group to prepare a polymer that is a component of a pre-synthesized main chain. Examples thereof include a method of reacting the functional group-modified polymer with the active end of the polymer obtained by polymerizing a monomer as a constituent unit of the side chain. Among these production methods, the weight average molecular weight and vinyl content of the main chain and side chains of the conjugated diene-based graft polymer, the number of side chains, etc. can be freely controlled, and a desired functional group can be easily introduced. Therefore, a method of reacting the functional group-modified polymer, which is a constituent element of the main chain, with the active end of the polymer obtained by polymerizing a monomer, which is a constituent unit of the side chain, is preferable.

As a method for producing the conjugated diene-based graft polymer of the present invention, a production method including the following steps (A-1) and (B) is preferable.

(A-1) A functional group-modified conjugated diene-based polymer having an active terminal polymer (I) represented by the following formula (I) and a portion containing a functional group represented by the following formula (II) as a branched chain (A-1). Step of reacting with F) to prepare a conjugated diene-based graft polymer (G)

PX (I)
(In formula (I), P represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and X represents the active end of anionic polymerization).

(In formula (II), V represents an alkoxy group or a hydroxyl group, Z is Si, Sn, Ge, Pb, P, B, or Al, and 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, and 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. ); And (B) A step of recovering the obtained conjugated diene-based graft polymer.

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 portion derived from all the monomer units including the conjugated diene unit constituting the main chain.

[Step (A-1)]
The active terminal polymer (I) used in the above step (A-1) can be produced by using a known polymerization method. For example, the active terminal weight is obtained by anionic polymerization of the monomer in the presence of a polar compound, if necessary, using an anionically polymerizable active metal or active metal compound as an initiator in a solvent inert to the polymerization terminal. Coalescence (I) can be obtained. The P of this active terminal polymer (I) becomes the side chain (b) of the graft polymer obtained in the present invention.

Specific examples and preferred embodiments of the monomer that is the monomer unit constituting the active terminal polymer (I), and specific examples and preferred embodiments of the monomer unit contained in the active terminal polymer (I). The description of the above is the same as that of the side chain (b) of the conjugated diene-based graft polymer.

As the anionic polymerizable active metal or active metal compound, an organic alkali metal compound is preferable, and an organic lithium compound is more preferable. Examples of the organic lithium compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.

Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; 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 conjugated diene units without inactivating the reaction. Examples of 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 conjugated diene-based graft polymer of the present invention. 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 the same as that for the side chain (b) of the graft polymer of the present invention.

In the above step (A-1), 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 of the present invention.

Specific examples, preferred examples, and suitable contents of conjugated diene, which is a monomer unit constituting the unmodified conjugated diene polymer (F'), and monomers other than conjugated diene (aromatic vinyl). Specific examples, preferred examples, suitable contents and the like of the compound) are the same as those relating to the main chain (a) of the conjugated diene-based graft polymer. Further, the description of the weight average molecular weight (Mw), vinyl content, preferred embodiment of Tg, etc. of the unmodified conjugated diene polymer (F') is the same as the description regarding the main chain (a) of the conjugated diene graft polymer. is there.

As the 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. For example, 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.

Water is usually used as the dispersion medium. 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.

Examples of the radical polymerization initiator 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'). Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, turpinolene, γ-terpinene, α-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. Examples of the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.

After the polymerization reaction is stopped, an anti-aging agent may be added if necessary. After terminating the polymerization reaction, 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 nitric acid, sulfuric acid and the like are used as necessary. 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. At the time of solidification, if necessary, latex and an emulsified dispersion may be mixed in advance and recovered as an oil-expanded unmodified conjugated diene polymer (F').

As the above solution polymerization method, which is an example of a method for producing an unmodified conjugated diene polymer (F'), a known or known method can be applied. For example, using a Ziegler-based catalyst, a metallocene-based catalyst, or an anionically polymerizable active metal or active metal compound as an initiator in a solvent, a single amount containing a conjugated diene, optionally in the presence of a polar compound. Polymerize the body.

Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Examples include aromatic hydrocarbons such as toluene and xylene.

As the above-mentioned initiator, an anionic polymerizable active metal or an active metal compound is preferable, and an anionic polymerizable active metal compound is more preferable.

Examples of anionic polymerizable active metals 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.

As the anionic polymerizable active metal compound, an organic alkali metal compound is preferable. Examples of 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. Among these organic alkali metal compounds, 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 polymer.

When an organic alkali metal compound is used as an initiator, 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 conjugated diene units without inactivating the reaction. Examples of 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. Examples of 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.

By modifying the unmodified conjugated diene-based polymer (F') with a functional group, the functional group-modified conjugated diene-based 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 unsaturated bond contained in the unmodified conjugated diene-based 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 unsaturated bond contained in an unmodified conjugated diene polymer (F') with a platinum compound-containing catalyst. And 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. Among these production methods, from the viewpoint of availability of modification reagents and catalysts and production cost, a method of radical addition reaction of a compound having a mercapto group (-SH) is preferable, and the obtained functional group-modified conjugated diene system weight is preferable. From the viewpoint of the stability of the coalescence (F), 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 unsaturated bond contained in the unmodified conjugated diene-based polymer (F'). As a method, a method of radical addition reaction of the silane compound (IV) represented by the following formula (IV) to the carbon-carbon unsaturated bond contained in the unmodified conjugated diene-based polymer (F') is preferable.

(In formula (IV), R ⁴ represents a divalent alkylene group having 1 to 6 carbon atoms, and R ⁵ ^{and R 6} are independently aryl groups having 6 to 12 carbon atoms and alkyl having 1 to 12 carbon atoms, respectively. Indicates a group or hydrogen atom, n is an integer of 1 to 3, and when n is 2 or more, R ⁵ may be the same or different, and when 3-n is 2 or more, R ⁶ may be the same. It may be different.)

Examples of the silane compound (IV) include mercaptomethylenemethyldiethoxysilane, mercaptomethylenetriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, and 2-. Mercaptoethylethoxydimethylsilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxyethylsilane, 3-mercapto Examples thereof include propyldiethoxyethylsilane, 3-mercaptopropylmethoxydimethylsilane, and 3-mercaptopropylethoxydimethylsilane. These silane compounds may be used alone or in combination of two or more.

The mercapto group (-SH) of the silane compound (IV) is derived from the silane compound (IV) by radical addition reaction to the carbon-carbon unsaturated bond contained in the unmodified conjugated diene polymer (F'). A functional group-modified conjugated diene-based 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.

(In formula (V), ^{the definitions of R 4} , R ⁵ , R ⁶ , and n are the same as in formula (IV).)

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.

Examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, and 1,1-bis (t-butylperoxy). -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) Butan, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 1,1,3,3-tetra Methylbutyl hydroperoxide, dit-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-) Butyl peroxy) hexane, 2.5-hexanoyl peroxide, lauroyl peroxide, succinic peroxide, benzoyl peroxide and its substitutions, 2,4-dichlorobenzoyl peroxide, metattle oil peroxide, diisopropyl peroxy Dicarbonate, t-Butyl-2-ethylhexanoate, di-2-ethylhexyl peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylper Oxyacetate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxyoctanoate, t-butylperoxy3,3,5-trimethylhexanoate, t-butylper Oxylaurate, t-butylperoxycarbonate, t-butylperoxybenzoate, t-butylperoxyisobutyrate and the like can be mentioned.

Examples of the azo compound 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. Among these organic solvents, 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.

Further, when the reaction for adding the modified compound is carried out by the above method, an anti-aging 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. '-Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) (AO-40), 3,9-bis [1,1-dimethyl- 2- [3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO-80), 2,4-bis [(octylthio) methyl] -6-methylphenol (Irganox1520L), 2,4-bis [(dodecylthio) methyl] -6-methylphenol (Irganox1726), 2- [1- (2-hydroxy-) 3,5-Dit-pentylphenyl) ethyl] -4,6-dit-pentylphenyl acrylate (SumilizerGS), 2-t butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-Methylphenyl acrylate (Sumiiser GM), 6-t-butyl-4- [3- (2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxa Phosfepin-6-yloxy) propyl] -2-methylphenol (SumilizerGP), tris phosphite (2,4-dit-butylphenyl) (Irgafos168), dioctadecyl 3,3'-dithiobispropionate , Hydroquinone, p-methoxyphenol, N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (Nocrack 6C), bis (2,2,6,6-tetramethyl-4-piperidyl) Examples thereof include sebacate (LA-77Y), N, N-dioctadecyl hydroxylamine (IrgastabFS042), bis (4-t-octylphenyl) amine (Irganox5057) and the like.
The above-mentioned anti-aging agent may be used alone or in combination of two or more.

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 ° C 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.

It is derived from the alkoxysilane compound by hydrosilylating the carbon-carbon unsaturated bond contained in the unmodified conjugated diene polymer (F') in the presence of a platinum compound-containing catalyst and, if necessary, a co-catalyst used. As a method for introducing a functional group, a carbon-carbon unsaturated bond contained in an unmodified conjugated diene polymer (F') is introduced in the presence of a platinum compound-containing catalyst, preferably a platinum compound-containing catalyst and a co-catalyst. Below, a method of hydrosilylation with a silane compound (VI) represented by the following formula (VI) is preferable.

(In formula (VI), 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.)

Examples of the silane compound (VI) 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 derived from the silane compound (VI), specifically, by hydrosilylating the carbon-carbon unsaturated bond contained in the unmodified conjugated diene polymer (F') with the silane compound (VI). 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.

(In formula (VII), ^{the definitions of R 7} , R ⁸ , and n are the same as in formula (IV).)

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.
From the viewpoint of selectivity during hydrosilylation, 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 viewpoint 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.

As 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.

Examples of the ammonium salt of the inorganic acid 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.

Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, and glycolic acid. Among these, 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 1 × 10 -5} to 5 × 10 ^-1 mol per 1 mol of the silane compound (VI) is used from the viewpoint of reactivity, selectivity, cost and the like. Preferably, 1 × 10 ^-4 to 5 × 10 ^-1 mol is more preferable.

Although the hydrosilylation reaction proceeds without a solvent, a solvent can also be used. Examples of the solvent that can be used 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.

In 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.

From the viewpoint of affinity and stability of the obtained conjugated diene-based graft polymer with the polar material, Z in the above formula (II) is preferably Si or Sn, and more preferably Si.

From the viewpoint of affinity and stability of the obtained conjugated diene-based graft polymer with the polar material and reactivity in the coupling step described later, an alkoxy group is preferable as V in the above formula (II), and the number of carbon atoms is 1. Alkoxy groups of ~ 5 are more preferred, and methoxy groups and ethoxy groups are particularly preferred.

Although n in the above formula (II) is an integer satisfying the above formula (5), it is the reactivity in the coupling step described later and the number of side chains bonded to the branch point of the obtained conjugated diene graft polymer. From the viewpoint of control, 2 or more is preferable, 3 or more is more preferable, and it is particularly preferable that the valence is the same as Z.

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 polymer (F) is the functional group of the functional group V contained in the functional group-modified conjugated diene polymer (F). It is calculated from the following formula (10) using the equivalent amount (g / eq) and the number average molecular weight (Mn) converted to standard polystyrene.
(Average number of functional groups V in the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F)) = [(number average molecular weight Mn) / (molecular weight of styrene unit) × (conjugated diene and Average molecular weight of monomeric units other than conjugated diene contained as needed)] / (functional group equivalent of functional group V) (10)

The functional group equivalent of the functional group V contained in the functional group-modified conjugated diene polymer (F) is other than the conjugated diene bonded to one functional group V and the conjugated diene contained as necessary. It means the mass of the monomer. 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 functionally modified conjugated diene polymer (F). The average number of functional groups V contained in) may be appropriately set to a desired value. For example, the unmodified conjugated diene polymer (F') and the above-mentioned silane compound (IV) or silane compound (VI) may be set. ) May be mixed so that the mass ratio with) is 0.3 to 100.

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. When 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.

In the step (A-1), 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 in which the active terminal polymer (I) serving as a side chain is bonded to the hetero atom Z which is a branch point is formed (hereinafter referred to as the present invention). The reaction is called 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. By doing so, 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 conjugated diene-based graft polymer is formed.

The average number W of side chains (b) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is the active terminal polymer (I) in the coupling reaction and the functional group-modified conjugated diene-based polymer ( It can be adjusted to a desired range by the ratio of the charged amount of F). For example, when (amount of active terminal polymer (I) charged (number of moles)) / (amount of functional group-modified conjugated diene polymer (F) charged (number of moles)) = 4/1, the side chain (b) ) Has an average number of W of 4. However, the upper limit of W is the number of functional groups V per molecule of the functional group-modified conjugated diene polymer (F).

The molar ratio of (amount of active terminal polymer (I) charged) / (amount of functional group-modified conjugated diene polymer (F) charged) is directly bonded to the above-mentioned branch point per molecule of conjugated diene-based graft polymer. The average number W of the side chains (b) to be subjected may be appropriately set so as to be a desired value. For example, it is preferably 1 to 200, more preferably 2 to 100, and 3 to 50. It is more preferable to have. 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. For example, hexane or cyclohexane. , Saturated aliphatic hydrocarbons such as heptane, octane, decane, toluene, benzene and xylene, or aromatic hydrocarbons.
Further, a Lewis base may be added as an additive during the coupling reaction. 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; 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.

In the coupling reaction, 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). Further, as described above, 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. Further, 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 conjugated diene-based graft polymer are deteriorated, which is not preferable. The coupling rate is calculated by the following formula (10) using the sum of the peak areas of the components derived from the unreacted active terminal polymer (I) obtained by GPC measurement and all the peak areas.
(Coupling rate (%)) = [{(Sum of all peak areas)-(Peak area of components derived from active terminal polymer (I))} / (Sum of all peak areas)] × 100 ( 10)

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 amount and reaction time of the reagent used in the step of inactivating a part of at least one remaining functional group (unreacted functional group V) selected from the group consisting of the alkoxy group and the hydroxyl group to be used, and if necessary. It can be adjusted to a desired range depending on the type and amount of the polar compound to be added.
As a method for adjusting the number of functional groups (c) directly bonded to the branch point to a desired range, for example, the amount of the active terminal polymer (I) and the functional group-modified conjugated diene polymer (F) charged. The coupling reaction 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 conjugated diene-based graft polymer was 1 or more, and then (X / Y). Examples thereof include a method of inactivating a part of the remaining functional group (unreacted functional group V) described above so that the value is less than 1.

[Step (A-2)]
In the method for producing a conjugated diene-based graft polymer (G) of the present invention, after the 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) A step of inactivating a part of at least one remaining functional group (unreacted functional group V) selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene-based graft polymer. (Hereinafter referred to as the inactivation step);
Is a preferred embodiment.
When the alkoxy groups contained in the obtained conjugated diene-based graft polymer react with water or acid added in the recovery step (B) to generate hydroxyl groups and contain a relatively large number of hydroxyl groups, a large amount of these hydroxyl groups The inactivation step (A-2) is preferably performed before the recovery step (B) because it is considered that they are likely to cause a condensation reaction with each other.

Examples of the reagent used for inactivating the alkoxy group and the hydroxyl group (hereinafter, may be referred to as an inactivating reagent) 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, etc. 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 for the inactivation reaction to proceed rapidly.

Amount of Inactivating Reagent Used in Step (A-2) / Molar Ratio of Total Amount of Alkoxy Group and Hydroxyl Group Derived from Group V in Conjugated Diene Graft Polymer Obtained in Step (A-1) 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. When the amount of the inactivating reagent is small, the number of functional groups (c) directly bonded to the branch point cannot be adjusted to a desired range, and when the amount of the inactivating reagent is large, it is economical. Tends to get worse.

The inactivation reaction of 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. For example, hexane, cyclohexane, heptane, octane, etc. Saturated aliphatic hydrocarbons such as decane, toluene, benzene and xylene or aromatic hydrocarbons can be mentioned. Further, 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. After that, the inactivating reagent can be inactivated by adding a polymerization terminator such as methanol or isopropanol.

[Step (B)]
The method for producing a conjugated diene-based graft polymer of the present invention is
(B) Step of recovering the obtained conjugated diene-based graft polymer;
including.

In step (B), the obtained conjugated diene-based graft polymer of the present invention is recovered. The method for recovering the conjugated diene-based graft polymer is not particularly limited, but when a solution containing the conjugated diene-based graft polymer is obtained in step (A-1) or step (A-2), for example, it can be obtained. The above-mentioned conjugated diene-based graft polymer is isolated by pouring the solution into a poor solvent such as methanol to precipitate the conjugated diene-based graft polymer, or by washing the polymerization reaction solution with water, separating and drying. It can be recovered by.

[Polymer composition]
The polymer composition of the present invention contains the conjugated diene-based graft polymer of the present invention (hereinafter, also referred to as a conjugated diene-based graft polymer (α)). Further, the polymer composition may further contain a polymer (β) other than the conjugated diene-based graft polymer (α). The other polymer (β) may be a thermoplastic polymer (β1) or a curable polymer (β2).

Examples of the thermoplastic polymer (β1) 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 rubber modified resin; Acrylic rubbers; silicone rubbers; styrene-based thermoplastic polymers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM.

Examples of the curable polymer (β2) 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. Among these, 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 (β2) may be used alone or in combination of two or more.

When the polymer composition contains a conjugated diene-based graft polymer (α) and another polymer (β), the mass ratio of the conjugated diene-based graft polymer (α) to the other polymer (β). It is preferable that (α) / (β) is 1/99 to 99/1.

In addition, various 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. For example, when the other polymer (β) is a thermoplastic polymer (β1), such additives include, for example, reinforcing agents or fillers such as calcium carbonate, silica, carbon black, glass fiber, clay, and process oils. , Polyethylene glycol, glycerin, phthalates and other plasticizers can be used as additives. In addition, examples of other additives include heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, lubricants, and surfactants. Further, 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 (β1).
For example, when the other polymer (β) is a curable polymer (β2), 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 method of mixing a polymer substance according to the composition ratio of each component such as a conjugated diene-based graft polymer (α) and another polymer (β).

When the other polymer (β) is a thermoplastic polymer (β1), 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. In particular, in the present invention, a method of melt-kneading using these mixing devices is a preferable aspect.

When the other polymer (β) is a curable polymer (β2), for example, 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.

When the other polymer (β) is a thermoplastic polymer (β1), 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. By these methods, molded products, sheets, films and the like having various shapes can be obtained. In addition, 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.

When the other polymer (β) is a curable polymer (β2), 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 (β2) include, for example, an injection molding method and a compression molding method.

When the other polymer (β) is a thermoplastic polymer (β1), the molded product obtained from the polymer composition is used, for example, for automobile interior / exterior parts 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, food containers, packaging materials such as 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, elastic materials used for adhesives / adhesives, paper diapers, hoses, tubes, belts Various rubber products such as, medical supplies, etc. can be mentioned.

When the other polymer (β) is a curable polymer (β2), 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). Adhesives for, fiber-reinforced composite materials for transportation equipment such as automobiles, railroad vehicles, and aircraft, adhesives for fiber-reinforced composite materials for various sports equipment, etc.), assembly adhesives (transportation for automobiles, railroad vehicles, aircraft, etc.) 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.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, the physical characteristics of the conjugated diene-based graft polymer were evaluated by the following method.

(1) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)
By gel permeation chromatography (GPC), the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the conjugated diene-based graft polymer and the polymer at each stage of its production are determined. It was calculated in terms of standard polystyrene.
Equipment: GPC equipment "HLC-8220" manufactured by Tosoh Corporation
Separation column: "TSKgel SuperMultipore HZ-M (column diameter = 4.6 mm, column length = 15 cm)" manufactured by Tosoh Corporation (used by connecting two in series)
Eluent: Tetrahydrofuran Eluent Flow rate: 0.35 mL / min Column temperature: 40 ° C
Detection method: Differential refractometer (RI)
Injection volume: 10 μl
Concentration: 1 mg / 1 cc (conjugated diene graft polymer / THF)

(2) Vinyl content, styrene unit content ^{1 The} vinyl content and styrene unit content of the conjugated diene-based graft polymer and the polymer at each stage of its production were calculated by 1 H-NMR. The vinyl content was calculated from the area ratio of the double bond peak derived from the vinylized conjugated diene unit and the double bond peak derived from the non-vinylized conjugated diene unit in the obtained spectrum, and converted to the styrene unit. The styrene unit content was calculated from the area ratio of the peak of the derived aromatic ring and the peak of the double bond derived from the conjugated diene unit.
Equipment: Nuclear magnetic resonance equipment "JNM-ECX400" manufactured by JEOL Ltd.
Solvent: Deuterated chloroform Measurement temperature: 50 ° C
Accumulation number: 1024 times

(3) Average number of Si atoms (branch points) per polymer molecule Y
The average number Y of Si atoms (branch points) per molecule of the conjugated diene-based graft polymer and the functional group-modified conjugated diene-based polymer (F) is the weight measured by an inductively coupled plasma mass spectrometer (ICP-MS). It is calculated from the following formula using the combined Si content (% by mass) and the number average molecular weight (Mn) in terms of standard polystyrene.
(Number of Si atoms per polymer molecule) = [(Si content (mass%)) / 100] x [(number average molecular weight Mn) / (molecular weight in styrene units) x (conjugated diene and optionally included) Average molecular weight of other monomeric units other than conjugated diene)] / Atomic weight of Si For Example 16, the average number Y of B atoms (branching points) per polymer molecule was determined by the same method.

(4) Average number (X / Y) of functional groups (c) per Si atom (branch point) contained in the conjugated diene-based graft polymer.
The average number (X / Y) of the functional group (c) (at least one selected from the group consisting of an alkoxy group and a hydroxyl group) per Si atom (branch point) contained in the conjugated diene-based graft polymer is the conjugated diene-based graft polymer. It is obtained from the results of measuring ²⁹ Si-NMR of the graft polymer. Specifically, the integral value obtained by multiplying the integrated value of Si having one functional group (c) bonded and Si having two functional groups (c) bonded by the number of functional groups is added up and integrated. Calculated by comparing with a simple sum of values.
Regarding Example 16, ^{by measuring 11} B-NMR, the average number (X / Y) of the functional groups (c) per B atom (branch point) contained in the conjugated diene-based graft polymer was obtained by the same method. Asked.

(5) Average number of functional groups (c) per molecule of conjugated diene-based graft polymer X
The average number X of the functional groups (c) per molecule of the conjugated diene-based graft polymer is the average number of functional groups (c) per Si atom (branch point) contained in the conjugated diene-based graft polymer and the above-mentioned conjugated diene. It is calculated from the following formula using the average number of Si atoms per molecule of the system graft polymer.
(Average number of functional groups (c) per molecule of conjugated diene-based graft polymer X) = (Average number of functional groups (c) per Si atom (branch point) contained in conjugated diene-based graft polymer) × (Average number of Si atoms per molecule of conjugated diene-based graft polymer)
In Example 16, the average number of functional groups (c) per B atom (branch point) contained in the conjugated diene-based graft polymer and the average number of B atoms per molecule of the conjugated diene-based graft polymer were used. The average number X of the functional groups (c) per molecule of the conjugated diene-based graft polymer was determined.

(6) Average number of side chains (b) per molecule of conjugated diene-based graft polymer W
The average number W of side chains (b) per molecule of the conjugated diene-based graft polymer is the active terminal polymer (b) that is a component of the side chain (b) of the conjugated diene-based graft polymer in the above-mentioned coupling step. It is calculated from the following formula using the charge amount (number of moles) per active terminal of I) and the charge amount (number of moles) of the functional group-modified conjugated diene polymer (F).
(Average number of side chains (b) per molecule of conjugated diene-based graft polymer W) = (Amount of active terminal polymer (I) charged per active end (number of moles) which is a component of the side chain (b) )) / (Amount of functional group-modified conjugated diene polymer (F) charged (number of moles))

(7) Average number of side chains (b) per Si atom (branch point) contained in the conjugated diene-based graft polymer (W / Y)
The average number (W / Y) of side chains (b) per Si atom (branch point) contained in the conjugated diene-based graft polymer is the average of the side chains (b) per molecule of the conjugated diene-based graft polymer. It is calculated from the following formula using the number W and the average number Y of Si atoms per molecule of the conjugated diene-based graft polymer.
(Average number of side chains (b) per Si atom contained in the conjugated diene-based graft polymer (W / Y)) = (Average number of side chains (b) per molecule of the conjugated diene-based graft polymer W) / (Average number of Si atoms per molecule of conjugated diene-based graft polymer Y)
In Example 16, the conjugated diene system uses the average number W of side chains (b) per molecule of the conjugated diene graft polymer and the average number Y of B atoms per molecule of the conjugated diene graft polymer. The average number (W / Y) of side chains (b) per B atom (branch point) contained in the graft polymer was determined.

(8) Coupling rate The coupling rate of the conjugated diene-based graft polymer is calculated by the following formula using the sum of the peak areas of the unreacted polymer components obtained by the above GPC measurement and all the peak areas.
(Coupling rate (%)) = [{((Sum of all peak areas)-(Peak area of components derived from active terminal polymer (I))} / (Sum of all peak areas)] × 100

(9) Stability The stability of the conjugated diene-based graft polymer was evaluated by the change in properties in the step of drying the polymer solution containing the conjugated diene-based graft polymer after completion of washing (step (5) below). A 100-fold amount of cyclohexane was added to the polymer vacuum-dried at 70 ° C. for 24 hours, and the mixture was shaken at room temperature for 12 hours, and then the insoluble matter was recovered by filtration and dried. The insoluble matter ratio (gel fraction) was calculated from the following formula, where the mass of the charged polymer was M1 and the mass of the insoluble matter after filtration and drying was M2, and the stability was evaluated by the following index.
(Gel fraction (%)) = (M2 / M1) x 100
A: Gel fraction after drying is less than 50% by mass B: Gel fraction after drying is 50% by mass or more

(10) Condensation Reactivity The affinity of the conjugated diene-based graft polymer with the polar material was evaluated by the condensation reactivity of the alkoxysilane group under acidic conditions. The conjugated diene-based graft polymer is dissolved in cyclohexane so that the solid content concentration is 10% by mass, mixed with a 1% by mass acetic acid aqueous solution at a weight ratio of 1: 1 and shaken at room temperature for 12 hours, and then insoluble (gel). Was visually confirmed, and the condensation reactivity was evaluated using the following indexes. It can be said that the condensation reactivity is higher when there is an insoluble matter, and the affinity with the polar material is higher.
A: With insoluble matter B: No insoluble matter

[Example 1]
(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, 2.9 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.3 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. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain an unmodified conjugated diene polymer (F'-1).

(Step (2))
Subsequently, 700 g of the unmodified conjugated diene polymer (F'-1) 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-1). Analysis of the obtained functional group-modified conjugated diene polymer (F-1) revealed that the main chain (a) of the conjugated diene graft polymer (G-1) described later contains the weight average molecular weight, vinyl content, and styrene unit. The amount can be calculated. The obtained functional group-modified conjugated diene polymer (F-1) has a weight average molecular weight of 26,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and Si atoms per polymer molecule. The average number was four. 1750 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-1) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-1) 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. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-1). By sampling and analyzing the polymer solution in the step (3), the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-1) described later can be determined. be able to. The weight average molecular weight of the obtained active terminal polymer (I-1) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.

(Step (4))
Subsequently, 7.0 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). 1480 g of the diluted solution was added, and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 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. Then, 21 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.

(Step (5))
Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft polymer (G-1). The weight average molecular weight of the obtained conjugated diene graft polymer (G-1) is 46,000, Mw / Mn is 1.5, the styrene unit content is 0% by mass, the coupling rate is 95%, and the polymer 1 The average number of Si atoms (branch points) per molecule is 4, the average number of functional groups (c) per polymer molecule is 0.4, and the average number of functional groups (c) per Si atom (branch point). The average number was 0.1, the average number of side chains (b) per polymer molecule was 4, and the average number of side chains (b) per Si atom (branch point) was 1. Table 1 shows the types and amounts of each reagent used in Example 1, and Table 3 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymer (G-1).

[Examples 2 to 14]
Conjugated diene graft polymer (G) 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. -2)-(G-14) were obtained. The molecular specifications and physical properties of the obtained conjugated diene-based graft polymers (G-2) to (G-14) are shown in Tables 3 and 4.

[Example 15]
(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, 2.9 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.3 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. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain an unmodified conjugated diene polymer (F'-15).

(Step (2))
Subsequently, 700 g of the unmodified conjugated diene polymer (F'-15) 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. over 2 hours, and then the mixture was stirred at 80 ° C. for 1 hour. After completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-15). Analysis of the obtained functional group-modified conjugated diene polymer (F-15) revealed that the main chain (a) of the conjugated diene graft polymer (G-15) described later contains the weight average molecular weight, vinyl content, and styrene unit. The amount can be calculated. The obtained functional group-modified conjugated diene polymer (F-15) has a weight average molecular weight of 26,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and Si atoms per polymer molecule. The average number was four. 1710 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-15) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-15) 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. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-15). By sampling and analyzing the polymer solution in the step (3), the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-15) described later can be determined. be able to. The weight average molecular weight of the obtained active terminal polymer (I-15) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.

(Step (4))
Subsequently, 7.0 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-15) obtained in step (2) were added to the solution containing the active terminal polymer (I-15) obtained in step (3). 1480 g of the diluted solution was added, and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 195 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, 21 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.

(Step (5))
Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft polymer (G-15). The weight average molecular weight of the obtained conjugated diene graft polymer (G-15) is 46,000, Mw / Mn is 1.5, the styrene unit content is 0% by mass, the coupling rate is 95%, and the polymer 1 The average number of Si atoms (branch points) per molecule is 4, the average number of functional groups (c) per polymer molecule is 0.4, and the average number of functional groups (c) per Si atom (branch point). The average number was 0.1, the average number of side chains (b) per polymer molecule was 4, and the average number of side chains (b) per Si atom (branch point) was 1. Table 4 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymer (G-15).

[Example 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, 2.9 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.3 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. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain an unmodified conjugated diene polymer (F'-16).

(Step (2))
Subsequently, 700 g of the unmodified conjugated diene polymer (F'-16) 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-16). Analysis of the obtained functional group-modified conjugated diene polymer (F-16) revealed that the main chain (a) of the conjugated diene graft polymer (G-16) described later contains the weight average molecular weight, vinyl content, and styrene unit. The amount can be calculated. The obtained functional group-modified conjugated diene polymer (F-16) has a weight average molecular weight of 26,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and B atoms per molecule of the polymer. The average number was four. 1680 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 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, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-16). By sampling and analyzing the polymer solution in the step (3), the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-16) described later can be determined. be able to. The weight average molecular weight of the obtained active terminal polymer (I-16) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.

(Step (4))
Subsequently, 7.0 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). 1480 g of the diluted solution was added, and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 195 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, 21 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.

(Step (5))
Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft polymer (G-16). The weight average molecular weight of the obtained conjugated diene graft polymer (G-16) is 46,000, Mw / Mn is 1.5, the styrene unit content is 0% by mass, the coupling rate is 95%, and the polymer 1 The average number of B atoms (branch points) per molecule is 4, the average number of functional groups (c) per polymer molecule is 0.4, and the average number of functional groups (c) per B atom (branch point). The average number was 0.1, the average number of side chains (b) per polymer molecule was 4, and the average number of side chains (b) per B atom (branch point) was 1. Table 4 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymer (G-16).

[Comparative Example 1]
(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, 2.9 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.3 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. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain an unmodified conjugated diene polymer (F'-17).

(Step (2))
Subsequently, 700 g of the unmodified conjugated diene polymer (F'-18) 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. Add 5.6 mL of a 2% xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ("PC072" manufactured by Polymer System) and 120 g of trimethylchlorosilane, and prepare them overnight. Stirred. Then, 20 g of dimethylchlorosilane was added dropwise thereto, and then the mixture was gradually heated until the internal temperature reached 70 ° C., and the mixture was stirred under reflux while maintaining the internal temperature at 70 ° C. for 24 hours. After completion of stirring, the mixture was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-17). Analysis of the obtained functional group-modified conjugated diene polymer (F-17) revealed that the main chain (a) of the conjugated diene graft polymer (G-17) described later contains the weight average molecular weight, vinyl content, and styrene unit. The amount can be calculated. The obtained functional group-modified conjugated diene polymer (F-17) has a weight average molecular weight of 26,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and Si atoms per polymer molecule. The average number was four. 1680 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 set to 50 ° C. under stirring conditions. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-17). By sampling and analyzing the polymer solution in the step (3), the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-17) described later can be determined. be able to. The weight average molecular weight of the obtained active terminal polymer (I-17) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.

(Step (4))
Subsequently, 7.0 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-17) obtained in step (2) were added to the solution containing the active terminal polymer (I-17) obtained in step (3). 1480 g of the diluted solution was added, and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 195 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours. Then, 21 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.

(Step (5))
Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft polymer (G-17). The weight average molecular weight of the obtained conjugated diene graft polymer (G-17) is 46,000, Mw / Mn is 1.5, the styrene unit content is 0% by mass, the coupling rate is 99%, and the polymer 1 The average number of Si atoms (branch points) per molecule is 4, the average number of functional groups (c) per polymer molecule is 0, and the average number of functional groups (c) per Si atom (branch point). The average number of side chains (b) per molecule of the polymer was 4, and the average number of side chains (b) per Si atom (branch point) was 1. Table 4 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymer (G-17).

[Comparative Example 2]
(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, 2.9 g of tetrahydrofuran and 1250 g of butadiene were sequentially added and polymerized for 1 hour. Then, 3.3 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. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain an unmodified conjugated diene polymer (F'-18).

(Step (2))
Subsequently, 700 g of the unmodified conjugated diene polymer (F'-18) 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-18). Analysis of the obtained functional group-modified conjugated diene polymer (F-18) revealed that the main chain (a) of the conjugated diene graft polymer (G-18) described later contains the weight average molecular weight, vinyl content, and styrene unit. The amount can be calculated. The obtained functional group-modified conjugated diene polymer (F-18) has a weight average molecular weight of 26,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and Si atoms per polymer molecule. The average number was four. 1750 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-18) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-18) 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. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-18). By sampling and analyzing the polymer solution in the step (3), the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-18) described later can be determined. be able to. The weight average molecular weight of the obtained active terminal polymer (I-18) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.

(Step (4))
Subsequently, 7.0 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-18) obtained in step (2) were diluted in a solution containing the active terminal polymer (I-18) obtained in step (3). 1480 g of the solution was added and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 10 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.

(Step (5))
Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. When the polymer solution after washing was vacuum-dried at 70 ° C. for 24 hours, the conjugated diene-based graft polymer (G-18) was insolubilized and the gel fraction was 80% by mass or more. The weight average molecular weight of the obtained conjugated diene graft polymer (G-18) is 46,000, Mw / Mn is 1.5, the styrene unit content is 0% by mass, the coupling rate is 95%, and the polymer 1 The average number of Si atoms (branch points) per molecule is 4, the average number of functional groups (c) per polymer molecule is 8, and the average number of functional groups (c) per Si atom (branch point). The average number of side chains (b) per polymer molecule was 1.0, and the average number of side chains (b) per Si atom (branch point) was 1 (weight average molecular weight). , Mw / Mn, vinyl content, styrene unit content, average number of Si atoms (branch points) per polymer molecule, average number of functional groups (c) per polymer molecule, Si atoms (branch points) The average number per unit is a value obtained by measuring the polymer obtained by drying the polymer solution obtained in step (4) at room temperature and under normal pressure). Table 4 shows the molecular specifications and physical properties of the obtained conjugated diene-based graft polymer (G-18).

The types and amounts of the reagents used in the steps (1) to (5) in Examples 1 to 14 are shown in Tables 1 and 2 below, and the conjugated diene systems obtained in Examples 1 to 16 and Comparative Examples 1 and 2 are shown. The physical characteristics of the graft polymer are shown in Tables 3 and 4.

In Tables 1 and 2, the abbreviations are as follows: SBL: sec-butyllithium THF: tetrahydrofurant-BPOP: t-butylperoxypivalate Bd: 1,3-butadieneIp: isoprene St: styrene MPTES: (3- Mercaptopropyl) Triethoxysilane MFPS: (3-mercaptopropyl) Trimethoxysilane

From Tables 3 and 4, the conjugated diene system of Examples 1 to 16 in which the average number (X / Y) of the functional groups (c) per Si atom (branch point) is in the range of 0 <(X / Y) <1. Since the graft polymer has a high condensation reactivity, it can be seen that it has an excellent affinity with polar materials. Furthermore, it can be seen that the polymer solution containing the conjugated diene-based graft polymer has high stability because the ratio of the insoluble matter is small in the step of drying the polymer solution after the completion of washing.
On the other hand, the conjugated diene-based graft polymer of Comparative Example 1 in which the average number (X / Y) of the functional groups (c) per Si atom (branch point) is 0 has a low condensation reactivity, and thus is a polar material. Inferior in affinity with. Further, the conjugated diene-based graft polymer of Comparative Example 2 in which the average number (X / Y) of the functional groups (c) per Si atom (branch point) is in the range of 1 <(X / Y) is a polymer solution. In the process of drying the mixture, the ratio of insoluble matter was high and it was difficult to take it out.

The conjugated diene-based graft polymer of the present invention has excellent affinity with polar materials and has high stability. Therefore, interior and exterior parts for automobiles, electrical / electronic parts, packaging materials, sporting goods, daily miscellaneous goods, etc. It can be effectively used in a wide range of fields such as laminating materials, elastic materials, various rubber products, medical products, various adhesives, and various coating primers.

Claims

In the main chain (a) composed of a polymer containing a conjugated diene unit,
A side chain (b) consisting of a polymer containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units via one heteroatom having a valence of 3 or more, which is a branching point. ) Is a conjugated diene-based graft polymer bonded to it.
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 functional groups (c) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer and the average number Y of branch points per molecule of the conjugated diene-based graft polymer are the following formula (2);
0 <(X / Y) <1 (2)
Satisfy the relationship,
Conjugated diene graft polymer.
The average number X of the functional groups (c) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is the following formula (3);
0 <X ≦ 10 (3)
The conjugated diene-based graft polymer according to claim 1, which satisfies the above relationship.
The conjugated diene-based graft polymer according to claim 1 or 2, wherein the heteroatom is Si.
The average number W of side chains (b) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer and the average number Y of branch points per molecule of the conjugated diene-based graft polymer are the following formula (4);
0.5 ≤ (W / Y) (4)
The conjugated diene-based graft polymer according to any one of claims 1 to 3, which satisfies the above relationship.
(A-1) The active terminal polymer represented by the following formula (I) and PX (I)
(In formula (I), P represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and X represents the active end of anionic polymerization). ,
A step of producing a conjugated diene-based graft polymer by reacting with 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.

(In formula (II), V represents an alkoxy group or a hydroxyl group, Z is Si, Sn, Ge, Pb, P, B, or Al, and 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, and 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. ); And (B) Step of recovering the obtained conjugated diene-based graft polymer;
The method for producing a conjugated diene-based graft polymer according to claim 1.
Further, before the step (B),
(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;
5. The method for producing a conjugated diene-based graft polymer according to claim 5.
The method for producing a conjugated diene-based graft polymer according to claim 5 or 6, wherein Z in the formula (II) is Si.
The method for producing a conjugated diene-based graft polymer according to any one of claims 5 to 7, wherein the functional group V in the formula (II) is an alkoxy group.
The conjugated diene-based graft polymer according to any one of claims 1 to 4, which is obtained by the production method according to any one of claims 5 to 8.
A polymer composition containing the conjugated diene-based graft polymer according to any one of claims 1 to 4 and 9.
A molded product obtained by molding the polymer composition according to claim 10.