JPWO2020045316A1 - Polymer modifiers, methods for producing modified conjugated diene polymers, modified conjugated diene polymers, rubber compositions, tires and rubber belts. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modifier for a polymer and a modified conjugated diene polymer capable of obtaining a modified conjugated diene polymer composition excellent in various properties such as processability, mechanical strength, abrasion resistance and low fuel consumption. The purpose is. A polymer modifier of the present invention is characterized by containing a compound represented by the following general formula (1). Z represents an oxygen atom or a sulfur atom. A1 and A2 represent a 6-membered ring aromatic heterocyclic group or a 6-membered ring aromatic heterocyclic group containing at least one nitrogen atom as a constituent element of the ring. R1 and R2 are saturated or unsaturated 3- to 12-membered ring heterocyclic groups that are bonded to the carbon atoms of A1 and A2 and each independently has an unsubstituted or substituent, and one nitrogen atom is heterocyclic. One hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the heterocycle. m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. [Selection diagram] None

Description

The present invention relates to a modifier for a polymer, a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, a rubber composition, a tire and a rubber belt.

Compounds such as aromatic amines and alkoxysilanes are generally known as polymer modifiers.

As an example of modifying a high cisdiene rubber with a denaturing agent, cis-1,4-polybutadiene is produced using a titanium compound having a cyclopentadienyl skeleton as a catalyst, and then 4,4'-bis (diethylamino) benzophenone is used. A method of reacting and denaturing is known (see Patent Document 1).

A method for producing a modified diene rubber by reacting a diene rubber having an active alkali metal terminal with a nitroamino compound, a nitro compound, a nitroalkyl compound or the like is known (see Patent Documents 2 to 4). ..
A method of reacting an amine compound, an imide compound, a quinone compound, a thiazole compound, a sulfenamide compound, or the like after producing polybutadiene to modify the polybutadiene, or a method of using an alkoxysilane compound as a modifier is known. (See Patent Documents 5 to 9).

A rubber composition containing polybutadiene rubber (BR) or styrene-butadiene rubber (SBR) as the main component and other natural rubbers, etc., makes the best use of its characteristics, and mainly uses materials for tires, crawler of crawler type traveling device, etc. It is industrially produced and used as an industrial rubber belt or the like (see Patent Documents 10 and 11).

Japanese Unexamined Patent Publication No. 2000-8617 Japanese Unexamined Patent Publication No. 63-139902 Japanese Unexamined Patent Publication No. 63-278946 Japanese Unexamined Patent Publication No. 63-278947 Japanese Unexamined Patent Publication No. 2001-139633 Japanese Unexamined Patent Publication No. 2001-139634 JP-A-2002-30110 Patent No. 05217377 Patent No. 04376590 Japanese Unexamined Patent Publication No. 2007-23266 Japanese Unexamined Patent Publication No. 2004-346220

However, a modifier for a polymer and a modified conjugated diene polymer capable of obtaining a modified conjugated diene polymer composition having excellent various properties such as processability, mechanical strength, abrasion resistance and low fuel consumption have been proposed. There wasn't.
Therefore, the present invention provides a modifier for a polymer and a modified conjugated diene polymer capable of obtaining a modified conjugated diene polymerization composition object having excellent various properties such as processability, mechanical strength, abrasion resistance and low fuel consumption. The purpose is to provide. The present invention also provides a method for producing a modified conjugated diene polymer capable of obtaining a modified conjugated diene polymer composition having excellent various properties such as processability, mechanical strength, abrasion resistance and low fuel consumption. The purpose is. Another object of the present invention is to provide a rubber composition, a tire and a rubber belt having excellent various characteristics such as workability, mechanical strength, wear resistance and fuel efficiency.

The present inventor has completed the present invention as a result of diligent research to solve the above problems. The present invention relates to the following.

[1] A polymer modifier containing a compound represented by the following general formula (1).

（Ｚは酸素原子又は硫黄原子を示す。
Ａ^１及びＡ^２は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す。
Ｒ^１及びＲ^２は、Ａ^１及びＡ^２の炭素原子と結合しており、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を複素環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を複素環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に０〜４の整数で、ｍ＋ｎ≧１を満たす数値である。）
［２］前記式（１）のｍ及びｎが１である、［１］の重合体用変性剤。
［３］前記式（１）のＲ^１及びＲ^２中の窒素原子がＡ^１及びＡ^２の炭素原子と結合している、［１］又は［２］の重合体用変性剤。
［４］前記式（１）のＲ^１及びＲ^２がＡ^１及びＡ^２のパラ位の炭素原子と結合している、［１］〜［３］の重合体用変性剤。
［５］前記式（１）のＲ^１及びＲ^２は、各々独立に、窒素原子１個又は２個を環の構成成分に含む飽和又は不飽和の５〜６員環複素環基、窒素原子１個と酸素原子１個を環の構成成分に含む飽和の５〜６員環複素環基及び窒素原子１個と硫黄原子１個を環の構成成分に含む飽和の５〜６員環複素環基からなる群より選ばれる複素環基である、［１］〜［４］の重合体用変性剤。
［６］前記式（１）のＲ^１及びＲ^２は、各々独立に、無置換又は置換基を有し、置換基は各々独立に、炭素数１〜１２の直鎖状又は分岐状のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜６の直鎖状又は分岐状のハロゲン化アルキル基、炭素数1〜１２の直鎖状又は分岐状のアルキル基で置換されたアミノ基、窒素原子を１個以上含む３〜１２員環複素環基、炭素数１〜６のアルコキシ基及びアリール基からなる群より選択される置換基である、［１］〜［５］の重合体用変性剤。
［７］希土類金属化合物及び／又はアルカリ金属化合物を用いて共役ジエン化合物を重合させて共役ジエン重合体を得る工程と、
前記共役ジエン重合体と［１］〜［６］の重合体用変性剤とを反応させて変性共役ジエン重合体を得る工程と、を有する、変性共役ジエン重合体の製造方法。
［８］前記希土類金属化合物は、下記の一般式（７）で表される非メタロセン型金属化合物である、［７］の変性共役ジエン重合体の製造方法。

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the heterocycle, and one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the heterocycle.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. )
[2] The polymer modifier of [1], wherein m and n of the formula (1) are 1.
[3] The polymer modifier of [1] or [2], wherein the nitrogen atom in ^{R 1} and R ² of the above formula (1) ^{is bonded to the carbon atom of A 1} and A ^2.
[4] The polymer modifier of [1] to [3], ^{wherein R 1} and R ² of the above formula (1) are bonded to carbon atoms at the para positions of A ¹ and A ^{2.
[5] R 1} and R ² of the above formula (1) are saturated or unsaturated 5- to 6-membered heterocyclic groups and nitrogen atoms containing one or two nitrogen atoms as ring constituents, respectively. Saturated 5- to 6-membered ring heterocyclic groups containing 1 and 1 oxygen atom as ring constituents and saturated 5- to 6-membered ring heterocycles containing 1 nitrogen atom and 1 sulfur atom as ring constituents The modifier for a polymer of [1] to [4], which is a heterocyclic group selected from the group consisting of groups.
^{[6] R 1} and R ² of the above formula (1) each independently have an unsubstituted or substituent, and each of the substituents independently has a linear or branched alkyl having 1 to 12 carbon atoms. Amino substituted with a group, a cycloalkyl group having 3 to 12 carbon atoms, a linear or branched alkyl halide group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 12 carbon atoms. The weight of [1] to [5], which is a substituent selected from the group consisting of a group, a 3- to 12-membered ring heterocyclic group containing one or more nitrogen atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group. Denaturer for coalescence.
[7] A step of polymerizing a conjugated diene compound using a rare earth metal compound and / or an alkali metal compound to obtain a conjugated diene polymer.
A method for producing a modified conjugated diene polymer, which comprises a step of reacting the conjugated diene polymer with the modifiers for polymers [1] to [6] to obtain a modified conjugated diene polymer.
[8] The method for producing a modified conjugated diene polymer according to [7], wherein the rare earth metal compound is a non-metallocene type metal compound represented by the following general formula (7).

（但し、Ｒ^３、Ｒ^５は炭素数１〜１２の炭化水素基を表し、Ｒ^４は水素又は炭素数１〜１２の炭化水素基を表し、Ｏは酸素原子を表し、Ｍは希土類金属原子を表す。）
［９］［７］又は［９］の変性共役ジエン重合体の製造方法により製造される、変性共役ジエン重合体。
［１０］共役ジエン重合体の末端に下記一般式（１）で示される化合物由来の構造を有する変性共役ジエン重合体。

(However, R ³ and R ⁵ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁴ represents hydrogen or hydrocarbon groups having 1 to 12 carbon atoms, O represents an oxygen atom, and M represents a rare earth metal atom. Represents.)
[9] A modified conjugated diene polymer produced by the method for producing a modified conjugated diene polymer according to [7] or [9].
[10] A modified conjugated diene polymer having a structure derived from a compound represented by the following general formula (1) at the end of the conjugated diene polymer.

（Ｚは酸素原子又は硫黄原子を示す。
Ｒ^１及びＲ^２は、各々独立に、無置換又は置換基を有する飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に０〜４の整数で、ｍ＋ｎ≧１を満たす数値である。）
［１１］［９］又は［１０］の変性共役ジエン重合体を含む、ゴム組成物。
［１２］［１１］のゴム組成物を用いたタイヤ。
［１３］［１１］のゴム組成物を用いたゴムベルト。

(Z represents an oxygen atom or a sulfur atom.
R ¹ and R ² are saturated 3- to 12-membered ring heterocyclic groups each independently having an unsubstituted or substituent, containing one nitrogen atom as a constituent element of the ring, and a nitrogen atom, an oxygen atom and sulfur. One heteroatom selected from the group consisting of atoms may be further contained as a constituent of the ring.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. )
[11] A rubber composition containing the modified conjugated diene polymer of [9] or [10].
[12] A tire using the rubber composition of [11].
[13] A rubber belt using the rubber composition of [11].

According to the present invention, a modifier for a polymer and a modified conjugated diene polymer capable of obtaining a modified conjugated diene polymer composition having excellent various properties such as processability, mechanical strength, abrasion resistance and low fuel consumption. Can be provided. Further, according to the present invention, a method for producing a modified conjugated diene polymer capable of obtaining a modified conjugated diene polymer composition having excellent various properties such as processability, mechanical strength, wear resistance and low fuel consumption can be obtained. Can be provided. Further, according to the present invention, it is possible to provide a rubber composition, a tire and a rubber belt having excellent various characteristics such as workability, mechanical strength, wear resistance and fuel efficiency.

Hereinafter, the polymer modifier, the method for producing the modified conjugated diene polymer, and the modified conjugated diene polymer of the present invention will be described.

<< Denaturer for polymer (1) >>
The "polymer modifier" includes a compound capable of modifying the end of the polymer, and the compound contained in the modifier chemically bonds with the end of the polymer to modify the end of the polymer (compound at the end). Introduce). The "polymer" is a compound in which a monomer is polymerized, and the polymer is not particularly limited, and examples thereof include a conjugated diene polymer.
The polymer modifier of the present invention is characterized by containing a compound represented by the following general formula (1).

（Ｚは酸素原子又は硫黄原子を示す。
Ａ^１及びＡ^２は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す。
Ｒ^１及びＲ^２は、Ａ^１及びＡ^２の炭素原子と結合しており、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に０〜４の整数で、ｍ＋ｎ≧１を満たす数値である。）

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the ring, and one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the ring.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. )

A modified conjugated diene polymer composition (rubber composition) obtained from a modified conjugated diene polymer modified by using such a modifier for a polymer has characteristics such as processability, mechanical strength, abrasion resistance, and low fuel consumption. It will be excellent in various characteristics.

The compound preferably has m and n of the general formula (1) of 1.
In the compound, it is preferable that the nitrogen atom in ^{R 1} and R ² of the general formula (1) is bonded to the carbon atom of ^{A 1} and A ^2.
In the compound, it is preferable that R ¹ and R ² of the general formula (1) are bonded to carbon atoms at the para positions of A ¹ and A ^2.

When A ¹ and A ² are 6-membered ring aromatic ring groups, the compound is preferably a compound represented by the following general formula (2).

（Ｚは酸素原子又は硫黄原子を示す。
Ｒ^１及びＲ^２は、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
Ｒ^１及びＲ^２中の窒素原子は、芳香環の炭素原子と結合している）

(Z represents an oxygen atom or a sulfur atom.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered ring heterocyclic groups each independently having an unsubstituted or substituent, containing one nitrogen atom as a constituent element of the ring, and a nitrogen atom and oxygen. One heteroatom selected from the group consisting of an atom and a sulfur atom may be further contained as a constituent of the ring.
The nitrogen atom in R ¹ and R ² is bonded to the carbon atom of the aromatic ring)

^{When A 1} and A ² are 6-membered ring aromatic heterocyclic groups containing at least one nitrogen atom as a constituent element of the ring, the compound has one nitrogen atom as a constituent element of the 6-membered ring aromatic heterocycle. It is preferable that the compound is selected from the group consisting of the following general formula (3), the following general formula (4), the following general formula (5), and the following general formula (6).

（Ｚは酸素原子又は硫黄原子を示す。
Ｒ^１及びＲ^２は、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
Ｒ^１及びＲ^２中の窒素原子は、６員環芳香族複素環基の炭素原子と結合している。）

(Z represents an oxygen atom or a sulfur atom.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered ring heterocyclic groups each independently having an unsubstituted or substituent, containing one nitrogen atom as a constituent element of the ring, and a nitrogen atom and oxygen. One heteroatom selected from the group consisting of an atom and a sulfur atom may be further contained as a constituent of the ring.
The nitrogen atom in R ¹ and R ² is bonded to the carbon atom of the 6-membered ring aromatic heterocyclic group. )

^{R 1} and R ² of the general formula (1) are saturated or unsaturated 5- to 6-membered ring heterocyclic groups containing 1 or 2 nitrogen atoms as ring constituents, 1 nitrogen atom and 1 oxygen atom. A group consisting of saturated or unsaturated 5- to 6-membered ring heterocyclic groups containing 1 nitrogen atom and 1 sulfur atom in the ring constituents. It is preferably a heterocyclic group selected from the above, and a saturated heterocyclic group and a thiazolyl group, an imidazolyl group, a pyrrolyl group and a saturated heterocyclic group selected from the group consisting of a pyrrolidyl group, a piperidyl group, a piperazyl group, a thiazolidyl group, a morpholic group and a thiomorpholic group. More preferably, it is an unsaturated heterocyclic group selected from the group consisting of pyrazolyl groups.
^{Further, R 1} and R ² of the general formula (1) may be a condensed bicyclic heterocyclic group in which another ring such as an aromatic ring is condensed with the 5- to 6-membered heterocyclic group, and may be a pyrrolidyl group. It is preferably an indrill group in which a 6-membered aromatic ring group is condensed.
^{R 1} and R ² of the general formula (1) may have different structures or the same structure, but it is preferable that they have the same structure.

^{Further, R 1} and R ² of the general formula (1) may be independently unsubstituted or have a substituent, but both are unsubstituted or both have a substituent. It is preferable to do so.

^{The substituents of R 1} and R ² of the general formula (1) are a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a direct group having 1 to 6 carbon atoms. A chain or branched alkyl halide group, a 3- to 12-membered ring heterocyclic group containing at least one amino group and a nitrogen atom substituted with a linear or branched alkyl group having 1 to 12 carbon atoms, carbon. It is preferably a substituent selected from the group consisting of an alkoxy group having a number of 1 to 6 and an aryl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms. Contains one or two linear or branched alkyl halides having 1-3 carbon atoms, amino groups substituted with linear or branched alkyl groups having 1 to 6 carbon atoms, and nitrogen atoms. More preferably, it is a substituent selected from the group consisting of a 5- to 12-membered ring heterocyclic group, an alkoxy group having 1 to 3 carbon atoms and a phenyl group.
The substituents on R ¹ and R ² may be different substituents or substituents having the same structure, but are preferably substituents having the same structure.
Further, R ¹ and R ² may have a plurality of substituents, and the plurality of substituents may be present on the same carbon. When having two alkoxy groups on the same carbon, the two alkoxy groups may form a cyclic structure.

Specifically, in the case of a saturated heterocyclic group, R ¹ and R ² are a piperidyl group, a 1-methylpiperazyl group, a 3- (diethylamino) pyrrolidyl group, a 4- (1-pyrrolidinyl) piperidyl group, and 4-tri. Fluoromethylpiperidyl group, pyrrolidyl group, thiomorpholyl group, morpholyl group, 3- (pyrrolidin-1-yl) piperidyl group, 2- (pyrrolidin-1-yl) piperidyl group, 1,4'-bipiperidyl group, 1,3' -Bipiperidyl group, 1,2'-bipiperidyl group, 4- (azetidine-1-yl)) piperidyl group, 3- (azetidine-1-yl)) piperidyl group, 2- (azetidine-1-yl)) piperidyl group , 4- (Aziridine-1-yl)) piperidine group, 3- (Aziridine-1-yl)) piperidine group, 2- (Aziridine-1-yl)) piperidine group, 1,3'bipyrrolidil group, 1,2 'Vipyrrolidyl group, N, N-diethylpiperidine-4-amino group, N, N-diethylpiperidine-3-amino group, N, N-diethylpiperidine-2-amino group, 3- (azetidine-1-yl) pyrrolidyl Groups, 2- (azetidine-1-yl) pyrrolidyl group, 3- (aziridine-1-yl) pyrrolidyl group, 2- (aziridine-1-yl) pyrrolidyl group and the like, but piperidyl group and 1-methylpiperazyl group , 3- (diethylamino) pyrrolidyl group, 4- (1-pyrrolidinyl) piperidyl group, 4-trifluoromethylpiperidyl group, pyrrolidyl group, thiomorpholyl group, morpholic group are preferable.

Specifically, in the case of an unsaturated heterocyclic group, R ¹ and R ² are a thiazolyl group, a thiadiazolyl group, an imidazolyl group, a 1-methylimidazolyl group, a 1-phenylimidazolyl group, a 1-methylbenzoimidazolyl group, 1 -Phenylbenzoimidazolyl group, pyrazolyl group, oxazolyl group, oxadiazolyl group 1-methylpyrazolyl group, 1-phenylpyrazolyl group, pyrrolyl group, indolyl group, isoindryl group and the like, but thiazolyl group, imidazolyl group, 1-methylimidazolyl group , 1-Phenylimidazolyl group, pyrazolyl group, 1-methylpyrazolyl group, pyrrolyl group and indolyl group are preferable.

^{(A 1} and A ² in the formula (1) are compounds having a 6-membered ring aromatic ring group, and R ¹ and R ² are compounds having a saturated 3- to 12-membered ring heterocyclic group).
Specific examples of the compound represented by the general formula (1) include bis (4- (piperidine-1-yl) phenyl) methanone and bis (4- (4-methylpiperazine-1-yl) phenyl) methanone. , Bis (4- (3- (diethylamino) pyrrolidine-1-yl) phenyl) methanone, bis (4- (4- (pyrrolidin-1-yl) piperidine-1-yl) phenyl) methanone, bis (4-( 4- (Trifluoromethyl) piperidine-1-yl) phenyl) methanone, bis (4- (pyrrolidin-1-yl) phenyl) methanone, bis (4-thiomorpholinophenyl) methanone, bis (4-morpholinophenyl) methanone , Bis (4- (1,4-dioxa-8-azaspiro [4,5] decane-8-yl) phenyl) methanone, phenyl (4- (4- (pyrrolidin-1-yl) phenyl) methanone, phenyl ( Examples thereof include 4- (4-pyrrolidin-1-yl) piperidine-1-yl) phenyl) methanone, but bis (4- (piperidin-1-yl) phenyl) metanone and bis (4- (4-methylpiperazine) -1-yl) phenyl) methanone, bis (4- (3- (diethylamino) pyrrolidine-1-yl) phenyl) methanone, bis (4- (4- (pyrrolidin-1-yl) piperidine-1-yl) phenyl ) Metanone, bis (4- (4- (trifluoromethyl) piperidine-1-yl) phenyl) metanone, bis (4- (pyrrolidin-1-yl) phenyl) methanone are preferred.

^{(A 1} and A ² in the formula (1) are 6-membered ring aromatic heterocyclic groups containing at least one nitrogen atom as a ring constituent element, and R ¹ and R ² are saturated 3- to 12-membered ring heterocycles. Compound that is a ring group)
Specific examples of the compound represented by the general formula (1) include bis (6- (pyrrolidin-1-yl) pyridin-3-yl) methanone and bis (6- (3-diethylamino) pyrrolidine-. 1-yl) Pyridine-3-yl) methanone, bis (6- (4- (pyrridine-1-yl) piperidine-1-yl) pyridin-3-yl) methanone, bis (6- (pyrrolidin-1-yl)) Pyridine-3-yl) methanone, bis (6- (3-diethylamino) pyrrolidine-1-yl) pyridin-3-yl) methanone, bis (6- (4- (pyrrolidin-1-yl) piperidine-1-yl) ) Pyridine-3 yl) methanone, bis (6- (piperidine-1-yl) pyridine-3-yl) methanone, bis (6- (4-methylpiperazine-1-yl) pyridine-3-yl) methanone, bis (6- (3- (diethylamino) pyrrolidine-1-yl) pyridin-3-yl) methanone, bis (6- (4- (pyrridine-1-yl) piperidine-1-yl) pyridin-3-yl) methanone , Bis (6- (4- (trifluoromethyl) piperidine-1-yl) pyridin-3-yl) methanone, bis (6- (pyrrolidin-1-yl) pyridin-3-yl) methanone, bis (6-yl) Thiomorpholinopyridine-3-yl) methanone, bis (6-morpholinopyridine-3-yl) methanone, bis (6- (1,4-dioxa-8-azaspiro [4,5] decane-8-yl) pyridine- Examples thereof include 3-yl) methanone, but bis (6- (pyrrolidin-1-yl) pyridin-3-yl) metanone and bis (6- (3-diethylamino) pyrrolidine-1-yl) pyridin-3-yl. ) Metanone and bis (6- (4- (pyrrolidin-1-yl) piperidine-1-yl) pyridin-3yl) metanone are preferable.

^{(A 1} and A ² in the formula (1) are compounds having a 6-membered ring aromatic ring group, and R ¹ and R ² are compounds having an unsaturated 3- to 12-membered ring heterocyclic group).
Specific examples of the compound represented by the general formula (1) include subclasses (A), (B), and (C) of the polymer modifier (2) and "classification (2)" described later. ), (D), (E), (F) and (G), and examples thereof include bis (4- (1-methyl-1H-imidazol-2-yl) phenyl) methanone and bis. (4- (1-Phenyl-1H-imidazol-2-yl) phenyl) methanone, bis (4- (1-methyl-1H-pyrazol-2-yl) phenyl) methanone, bis (4- (1H-pyrol-) 1-yl) phenyl) methanone, bis (4- (1H-imidazol-1-yl) phenyl) methanone, bis (4- (1-indolin-1-yl) phenyl) methanone, bis (4- (thiazole-2) -Il) Phenyl) Metanon is preferred.

^{(A 1} and A ² in the formula (1) are 6-membered ring aromatic heterocyclic groups containing at least one nitrogen atom as a constituent element of the ring, and R ¹ and R ² are unsaturated 3- to 12-membered groups. Compounds that are ring heterocyclic groups)
Specific examples of the compound represented by the general formula (1) include bis (6- (1-methyl-1H-imidazol-2-yl) pyridin-3-yl) metanone and bis (6--). (1-Phenyl-1H-imidazol-2-yl) Pyridine-3-yl) methanone, bis (6- (1-methyl-1H-pyrazol-2-yl) pyridin-3-yl) methanone, bis (6-yl) (1H-pyrrole-1-yl) Pyridine-3-yl) methanone, bis (6- (1H-imidazol-1-yl) pyridin-3-yl) methanone, bis (4- (1-indolin-1-yl)) ) Pyridine-3-yl) methanone, bis (6- (thiazole-2-yl) pyridin-3-yl) methanone and the like, but bis (6- (1-methyl-1H-imidazol-2-yl)) Pyridine-3-yl) metanone is preferred.

This makes it possible to obtain a modified conjugated diene polymer capable of providing a modified conjugated diene polymer composition having excellent various properties such as processability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone or in combination of two or more.

The modifier for a polymer of the present invention is a raw material (A) a halogenated benzophenone compound or a dihalogenated pyridine compound, a raw material (B) a saturated or unsaturated 3- to 12-membered ring heterocyclic compound, and a raw material (C) Periodic Table No. 1. It is preferably synthesized from an organic metal compound of an element selected from Group 1, an organic metal compound of an element selected from Group 10 and Group 11 of the periodic table of the catalytic component (D), and a coordinating compound.

Examples of the halogenated benzophenone compound of the raw material (A) include 2,2'-difluorobenzophenone, 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, and 3,3. '-Difluorobenzophenone, 3,3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4-fluorobenzophenone, 4-chlorolobenzophenone, 4-bromobenzophenone, 4,4' -Difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3', 5, Examples thereof include 5'-tetrabromobenzophenone.
Examples of the dihalogenated pyridine compound of the raw material (A) include 3-bromo-5-iodopyridine, 3-fluoro-5-chloropyridine, 3-fluoro-5-bromopyridine, 3-fluoro-5-iodopyridine, and 6-. Examples thereof include bromonicotinaldehyde, 2-bromo-5-cyanopyridine, 6-fluoronicotinaldehyde, 2-fluoro-5-cyanopyridine and the like.

Examples of the saturated 3- to 12-membered ring heterocyclic compound of the raw material (B) include piperidine, piperazine, pyrrolidine, piperidine, thiomorpholin, morpholin, and the like, such as piperidine, 1-methylpiperazine, and 3- (diethylamino). Pyrrolidine, 4- (1-pyrrolidinyl) piperidine, 4-trifluoromethylpiperidine, pyrrolidine, thiomorpholin, morpholin are preferred.
Examples of the unsaturated 3- to 12-membered ring heterocyclic compound of the raw material (B) include thiazole, imidazole, pyrazole, pyrrole, indole, and the like, such as thiazole, imidazole group, 1-methylimidazole, and 1-phenylimidazole. , Pyrazole, 1-methylpyrazole, pyrrole, indole are preferred.

Examples of the raw material (C) include sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide and the like.

Examples of the catalyst component (D) include copper acetate, copper 2-thiophene carboxylate, nickel chloride, bis (1,5-cycloteoctadiene) nickel, palladium acetate, bis (dibenzilidenacetone) palladium, and tetrakistriphenyl. Examples thereof include phosphine palladium, bipyridine, 1,10-phenanthroline, triphenylphosphine, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2- (dicyclohexylphosphine) biphenyl and the like.

The synthetic reaction of the modifier for polymer of the present invention may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not easily inhibit the reaction. For example, benzene, toluene, xylene, etc. Aromatic hydrocarbons such as ethylbenzene and cumene; non-polar proton solvents such as N, N-dimethylformamide, dimethyl sulfoxide and dimethylacetamide; ethers such as dioxane and 2-methyltetraxamine are preferable. Proton solvents are used. These solvents may be used alone or in combination of two or more.

The reaction temperature of the present invention is -100 to 100 ° C, preferably -80 to 30 ° C.

The polymer modifier of the present invention is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

<< Production method of modified conjugated diene polymer >>
Hereinafter, the method for producing the modified conjugated diene polymer of the present invention will be described.
The method for producing a modified conjugated diene polymer of the present invention includes a step of polymerizing a conjugated diene compound using a rare earth metal compound and / or an alkali metal compound to obtain a conjugated diene polymer, and the obtained conjugated diene polymer and the above-mentioned. It is characterized by having a step of reacting with the above-mentioned modifier for a polymer of the present invention to obtain a modified conjugated diene polymer.
By having such characteristics, it is possible to obtain a conjugated diene polymer capable of providing a modified conjugated diene polymer composition having excellent various properties such as processability, mechanical strength, wear resistance and fuel efficiency.

(Polymerization step of conjugated diene compound)
In this step, a conjugated diene compound is polymerized using a rare earth metal compound and / or an alkali metal compound to obtain a conjugated diene polymer.

The rare earth metal compound is not particularly limited as long as it is soluble in a non-polar organic solvent, and is not particularly limited. Examples thereof include alkoxides, rare earth metal carboxylates, and rare earth metal phosphates. The alkali metal compound is not particularly limited as long as it is soluble in a non-polar organic solvent, and examples thereof include organic alkali metal compounds.
From the viewpoint of obtaining high cis polybutadiene having many 1,4-cis structures, it is preferable to use a rare earth metal compound rather than an alkali metal compound.
As the rare earth metal, scandium, ittrium, lantern, placeodimium, neodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and the like can be preferably used.

The rare earth metal compound is preferably a non-metallocene type metal compound (diketone type rare earth metal complex) represented by the following general formula (7).

（但し、Ｒ^３、Ｒ^５は炭素数１〜１２の炭化水素基を表し、Ｒ^４は水素、または炭素数１〜１２の炭化水素基を表し、Ｏは酸素原子を表し、Ｍは希土類金属原子を表す。）

(However, R ³ and R ⁵ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁴ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, O represents an oxygen atom, and M represents a rare earth metal. Represents an atom.)

^{Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in R 3 to} R ⁵ of the general formula (7) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an s-butyl group. , Isobutyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethyl Saturated hydrocarbon groups such as propyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, unsaturated hydrocarbon groups such as vinyl, 1-propenyl, and allyl groups, Examples thereof include an alicyclic hydrocarbon group such as a cyclohexyl group, a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

In the general formula (7), it ^{is preferable that R 4} is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms. In particular, it ^{is preferable that R 4} is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ and R ⁵ are hydrocarbon groups having 1 to 6 carbon atoms.
Further, in the general formula (7), it ^{is preferable that R 4} is hydrogen or a saturated hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁵ are saturated hydrocarbon groups having 1 to 12 carbon atoms. In particular, R ⁴ is preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ³ and R ⁵ are preferably saturated hydrocarbon groups having 1 to 6 carbon atoms.

When the rare earth metal compound is a non-metallocene type metal compound, examples of the non-metallocene type metal compound include tris (2,2,6,6-tetramethyl-3,5-heptandionat) lanthanum and tris (2) as lanthanum compounds. , 2,6-trimethyl-3,5-heptandionat) lantern, tris (2,6-dimethyl-3,5-heptandionat) lantern, tris (3,5-heptanzionato) lantern, tris (2,4-pentandionato) ) Lantern, Tris (2,4-Hexanedionat) Lantern, Tris (1,5-dicyclopentyl-2,4-Pentandionato) Lantern, Tris (1,5-Dicyclohexyl-2,4-Pentandionato) Lanterns and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) lanterns and tris (2,6-dimethyl-3,5-heptandionat) lanterns are preferred.

Examples of non-metallocene-type metal compounds include gadolinium compounds such as gadolinium (2,2,6,6-tetramethyl-3,5-heptandionat) and gadolinium (2,2,6-trimethyl-3,5). -Heptandionato) Gadolinium, Tris (2,6-dimethyl-3,5-Heptandionato) Gadolinium, Tris (3,5-Heptandionato) Gadolinium, Tris (2,4-pentanedionato) Gadolinium, Tris (2,4-hexane) Examples thereof include gadolinium) gadolinium, tris (1,5-dicyclopentyl-2,4-pentanedolinium) gadolinium, and tris (1,5-dicyclohexyl-2,4-pentanedionat) gadolinium. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium and tris (2,6-dimethyl-3,5-heptandionat) gadolinium are preferred.

Examples of non-metallic metal compounds include praseodymium compounds such as praseodymium (2,2,6,6-tetramethyl-3,5-heptandionat) and praseodymium (2,2,6-trimethyl-3,5). -Heptandionato) praseodymium, tris (2,6-dimethyl-3,5-heptandionat) praseodymium, tris (3,5-heptandionat) praseodymium, tris (2,4-pentanedionato) praseodymium, tris (2,4-hexane) Zionato) praseodymium, tris (1,5-dicyclopentyl-2,4-pentanedionato) praseodymium, tris (1,5-dicyclohexyl-2,4-pentanedionat) praseodymium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) praseodymium and tris (2,6-dimethyl-3,5-heptandionat) praseodymium are preferred.

Examples of non-metallocene type metal compounds include, for example, neodymium compounds such as tris (2,2,6,6-tetramethyl-3,5-heptandionat) neodymium and tris (2,2,6-trimethyl-3,5). -Heptangionato) neodymium, tris (2,6-dimethyl-3,5-heptandionat) neodymium, tris (3,5-heptandionat) lantern, tris (2,4-pentanedionato) neodymium, tris (2,4-hexane) Examples thereof include neodymium) neodymium, tris (1,5-dicyclopentyl-2,4-pentanedionato) neodymium, and tris (1,5-dicyclohexyl-2,4-pentanedionato) neodymium. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) neodymium and tris (2,6-dimethyl-3,5-heptandionat) neodymium are preferred.

Examples of the non-metallocene type metal compound include terbium compounds such as terbium (2,2,6,6-tetramethyl-3,5-heptandionat) and terbium (2,2,6-trimethyl-3,5). -Heptandionato) terbium, tris (2,6-dimethyl-3,5-heptandionat) terbium, tris (3,5-heptandionat) terbium, tris (2,4-pentandionato) terbium, tris (2,4-hexane) Examples include terbium) terbium, tris (1,5-dicyclopentyl-2,4-pentanedionate) terbium, and tris (1,5-dicyclohexyl-2,4-pentanedionat) terbium. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) terbium and tris (2,6-dimethyl-3,5-heptandionat) terbium are preferred.

Examples of non-metallocene-type metal compounds include, for example, dysprosium compounds such as tris (2,2,6,6-tetramethyl-3,5-heptandionat) dysprosium and tris (2,2,6-trimethyl-3,5). -Heptandionato) dysprosium, tris (2,6-dimethyl-3,5-heptandionat) dysprosium, tris (3,5-heptandionat) dysprosium, tris (2,4-pentanedionato) dysprosium, tris (2,4-hexane) Examples thereof include dysprosium) dysprosium, tris (1,5-dicyclopentyl-2,4-pentane dysprosium) dysprosium, and tris (1,5-dicyclohexyl-2,4-pentane dynasto) dysprosium. Of these, dysprosium tris (2,2,6,6-tetramethyl-3,5-heptandionat) and dysprosium tris (2,6-dimethyl-3,5-heptandionat) are preferred.

Examples of the non-metallocene type metal compound include yttrium compounds such as yttrium (2,2,6,6-tetramethyl-3,5-heptandionat) yttrium and yttrium (2,2,6-trimethyl-3,5). -Heptandionato) yttrium, tris (2,6-dimethyl-3,5-heptandionat) yttrium, tris (3,5-heptandionat) yttrium, tris (2,4-pentanedionato) dysprosium, tris (2,4-hexane) Examples thereof include yttrium) yttrium, tris (1,5-dicyclopentyl-2,4-pentane dionato) yttrium, and tris (1,5-dicyclohexyl-2,4-pentane dionato) yttrium. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) yttrium and tris (2,6-dimethyl-3,5-heptandionat) yttrium are preferred.

The non-metallocene type metal compound may be used alone or in combination of two or more.

When the rare earth metal compound is a rare earth metal alkoxide, examples of the rare earth metal alkoxide include trimethoxylanthanum, triethoxylanthanum, trin-propoxylanthanum, triisopropoxylanthanum, tributoxylanthanum, and tripentoxylanthanum. Examples include trihexyloxylanthanum. Of these, triisopropoxylanthanum is preferred.

Examples of the rare earth metal alkoxide include, for gadolinium compounds, trimethoxygadolinium, triethoxygadolinium, trin-propoxygadolinium, triisopropoxygadolinium, tributoxygadolinium, tripentoxygadolinium, trihexyloxygadolinium, and the like. Be done. Of these, triisopropoxygadolinium is preferred.

Examples of the rare earth metal alkoxide include trimethoxypraseodymium, triethoxypraseodymium, trin-propoxypraseodymium, triisopropoxypraseodymium, tributoxypraseodymium, tripentoxypraseodymium, trihexyloxypraseodymium, and the like as praseodymium compounds. Be done. Of these, triisopropoxypraseodymium is preferred.

Examples of rare earth metal alkoxides include, for example, neodymium compounds such as trimethoxyneodymium, triethoxyneodymium, trin-propoxyneodymium, triisopropoxyneodymium, tributoxyneodymium, tripentoxyneodymium, and trihexyloxyneodymium. Be done. Of these, triisopropoxyneodymium is preferred.

Examples of the rare earth metal alkoxide include, for example, terbium compounds such as trimethoxyterbium, triethoxyterbium, trin-propoxyterbium, triisopropoxyterbium, tributoxyterbium, tripentoxyterbium, and trihexyloxyterbium. Be done. Of these, triisopropoxyterbium is preferred.

Examples of rare earth metal alkoxides include, for example, dysprosium compounds such as trimethoxydysprosium, triethoxydisprosium, trin-propoxydisprosium, triisopropoxydisprosium, tributoxydysprosium, tripentoxydysprosium, and trihexyloxydisprosium. Be done. Of these, triisopropoxide dysprosium is preferred.

Examples of the rare earth metal alkoxide include, for yttrium compounds, trimethoxyyttrium, triethoxyittrium, trin-propoxyittrium, triisopropoxyittrium, tributoxyittrium, tripentoxyittrium, trihexyloxyittrium, and the like. Be done. Of these, triisopropoxyyttrium is preferable.

The rare earth metal alkoxide compound may be used alone or in combination of two or more.

When the rare earth metal compound is a rare earth metal carboxylate, examples of the rare earth metal carboxylate include neodymium 2-ethylhexanoate, neodymium versatic acid, neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and picolin. Examples include neodymium acid, neodymium formic acid, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, and the like.

Among them, the rare earth metal carboxylate preferably includes neodymium 2-ethylhexanoate and neodymium versatic acid. The rare earth metal carboxylate may be used alone or in combination of two or more.

When the rare earth metal compound is a rare earth metal phosphate, the rare earth metal phosphate includes, for example, neodymdi (2-ethylhexyl) phosphate, neodymdibutyl phosphate, neodymdipentyl phosphate, neodymdihexyl phosphate, etc. Neodim diheptyl phosphate, neodym dioctyl phosphate, neodymdi (1-methylheptyl) phosphate, neodymdidecyl phosphate, neodymjidodecyl phosphate, neodymdioctadecyl phosphate, neodymiorail phosphate Salt, neodymdiphenyl phosphate, neodymdi (p-nonylphenyl) phosphate, neodymium butyl (2-ethylhexyl) phosphate, neodym (1-methylheptyl) (2-ethylhexyl) phosphate, neodym (2-ethylhexyl) Ethylhexyl) (p-nonylphenyl) phosphate, and the like.

Among them, the rare earth metal phosphate preferably includes neodymdi (2-ethylhexyl) phosphate. The rare earth metal phosphate (A) may be used alone or in combination of two or more.

When the alkali metal compound is an organic alkali metal compound, examples of the organic alkali metal compound include methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium. Among them, the organic alkali metal compound is preferably n-butyllithium. The organic alkali metal compound may be used alone or in combination of two or more.

Further, a catalyst other than the rare earth metal compound and the alkali metal compound may be used.
Examples of such a catalyst include organometallic compounds of Group 2, Group 12, and Group 13 elements of the Periodic Table.
As the organometallic compounds of Group 2, Group 12, and Group 13 elements of the Periodic Table, for example, organomagnesium, organozinc, organoaluminum, and the like are used. Of these compounds, preferred are dialkylmagnesium, alkylmagnesium chloride, alkylmagnesium bromide, dialkylzinc, trialkylaluminum, dialkylaluminum chloride, dialkylaluminum bromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide, alkylaluminum dichloride, Dialkylaluminum hydride and the like.

Specific compounds include alkylmagnesium halides such as methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, octylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, butylmagnesium iodide, and hexylmagnesium iodide. Can be mentioned.

Further, dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium and ethylhexylmagnesium can be mentioned.

Further, trialkyl zinc such as dimethylzinc, diethylzinc, diisobutylzinc, dihexylzinc, dioctylzinc and didecylzinc can be mentioned.

Further, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum can be mentioned.

In addition, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, organoaluminum halogen compounds such as ethylaluminum sesquichloride and ethylaluminum dichloride, and hydrided organoaluminum compounds such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum sesquihydrides are also available. Can be mentioned.

Moreover, you may use alumoxane as a catalyst.
Examples of the alumoxane are those obtained by contacting an organoaluminum compound with a condensing agent, and examples thereof include ^{a chain alumoxane represented by the general formula (-Al (R 62} ) O-) n, and a cyclic alumoxane. (R ⁶² is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization, which is 5 or more, preferably 10 or more). .. Examples of R ⁶² include methyl, ethyl, propyl and isobutyl groups, with methyl groups being preferred. Examples of the organoaluminum compound used as a raw material of alumoxane include trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, and a mixture thereof.

Among them, alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used.

Further, as the condensing agent, water is typically mentioned, but in addition to this, any one in which the above-mentioned trialkylaluminum undergoes a condensation reaction, for example, adsorbed water such as an inorganic substance, diol, or the like can be mentioned.

These organometallic compounds of Group 2, Group 12, and Group 13 elements of the Periodic Table can be used alone, but can also be used in combination of two or more.

Moreover, you may add the molecular weight modifier of the obtained conjugated diene polymer.
As the molecular weight modifier, at least one compound selected from the group consisting of (1) hydrogen, (2) metal hydride compound, and (3) hydrogenated organometallic compound can be used.

Examples of the (2) metal hydride compound of the molecular weight modifier in the present invention include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, and German. , Lithium hydride, sodium borohydride, lithium aluminum hydride, sodium hydride, and the like.

Further, as the (3) hydrogenated organic metal compound of the molecular weight modifier in the present invention, alkylboran such as methylboran, ethylboran, propylborane, butylboran and phenylboran, dimethylboran, diethylboran, dipropylborane, dibutylboran and diphenyl Dialkylboran such as borane, methylaluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, alkylaluminum dihydride such as phenylaluminum dihydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, Dialkylaluminum hydride such as dibutylaluminum hydride, diphenylaluminum hydride, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane , Tributylsilane, silanes such as triphenylsilane, methylgerman, ethylgerman, propylgerman, butylgerman, phenylgerman, dimethylgerman, diethylgerman, dipropylgerman, dibutylgerman, diphenylgerman, trimethylgerman, triethylgerman, tri Germans such as propylgerman, tributylgerman, and triphenylgerman, and the like can be mentioned.

Among these, diisobutylaluminum hydride and diethylaluminum hydride are preferable, and diisobutylaluminum hydride is particularly preferable.

An ionic compound composed of a non-coordinating anion and a cation may be added to the catalyst system of the present invention. It is necessary when the catalyst system of the present invention is a rare earth metal compound. Examples of non-coordinating anions include tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, and tetrakis (pentafluoro). Phenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (kisilyl) borate, triphenyl (pentafluorophenyl) borate, tris (penta) Fluorophenyl) (phenyl) borate, tridecahydride-7,8-dicarbundecaborate, tetrafluoroborate, hexafluorophosphate and the like can be mentioned.

On the other hand, examples of the cation include carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrosenium cation and the like.

Specific examples of the carbocation cation include trisubstituted carbocation cations such as triphenylcarbenium cation and tri-substituted phenylcarbenium cation. Specific examples of the tri-substituted phenylcarbenium cation include tri (methylphenyl) carbenium cation and tri (dimethylphenyl) carbenium cation.

Specific examples of ammonium cations include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation, N, N-dimethylanilinium cation, and N. , N-dialkylanilinium cations, N, N-2,4,6-pentamethylanilinium cations and other N, N-dialkylanilinium cations, di (isopropyl) ammonium cations, dicyclohexylammonium cations and other dialkylammonium cations Can be mentioned.

Specific examples of the phosphonium cation include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (dimethylphenyl) phosphonium cation and the like. Arylphosphonium cations can be mentioned.

As the above-mentioned ionic compound, those which are arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

Among them, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1'. -Dimethylpherosenium tetrakis (pentafluorophenyl) borate and the like are preferred. The ionic compound may be used alone, or two or more kinds may be used in combination.

There is no particular limitation on the order of addition of the catalyst components.

In the present invention, each catalyst component can be supported on an inorganic compound or an organic polymer compound for use.

As the conjugated diene compound monomer, 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2, 4-Hexadiene and the like can be mentioned. Of these, a conjugated diene compound monomer containing 1,3-butadiene as a main component is preferable. These conjugated diene compound monomer components may be used alone or in combination of two or more.

Further, the conjugated diene compound monomer and the α-olefin compound monomer may be used in combination. Examples of the α-olefin compound monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, styrene, and divinylbenzene. Of these, it is preferable to use styrene and a conjugated diene compound monomer in combination, and it is particularly preferable to use styrene and 1,3-butadiene in combination. One type of these α-olefin compound monomer components may be used alone, or two or more types may be used in combination.

The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) or solution polymerization using a conjugated diene compound monomer such as 1,3-butadiene as a polymerization solvent can be applied. Examples of the solvent for solution polymerization include aliphatic hydrocarbons such as butane, pentane, hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and the above. Examples thereof include olefin compounds and olefin hydrocarbons such as cis-2-butene and trans-2-butene.

Of these, benzene, toluene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is preferably used.

The polymerization temperature is preferably in the range of -30 to 150 ° C, more preferably in the range of 0 to 80 ° C, and particularly preferably in the range of 10 to 70 ° C. The polymerization time is preferably in the range of 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours, and even more preferably 10 minutes to 1 hour.

(Modification step of conjugated diene polymer)
In this step, the conjugated diene polymer obtained in the above step is reacted with the above-mentioned modifier for polymer of the present invention to obtain a modified conjugated diene polymer.
In this step, as the polymer modifier, one of the polymer modifiers as described above may be used alone, or two or more thereof may be used in combination.

The denaturation reaction is preferably carried out in an organic solvent.
The organic solvent used in the modification reaction can be freely used as long as it does not react with the conjugated diene polymer itself. Usually, the same solvent as that used for producing the conjugated diene polymer is used. Specific examples thereof include aromatic hydrocarbon solvents such as benzene, chlorobenzene, o-dichlorobenzene, toluene and xylene, and 5 carbon atoms such as n-heptane, n-hexane, n-pentane and n-octane. Examples thereof include an aliphatic hydrocarbon solvent of 10 to 10 and an alicyclic hydrocarbon solvent such as cyclohexane, methylcyclohexane, tetraline and decalin.

The temperature of the reaction solution for the denaturation reaction (a solution in which a conjugated diene polymer and a denaturant for a polymer are dispersed and dissolved in an organic solvent) is preferably in the range of -30 to 100 ° C, particularly in the range of 10 to 90 ° C. It is preferable to be in. If the temperature is too low, the denaturation reaction proceeds slowly, and if the temperature is too high, the polymer tends to gel. The time of the denaturation reaction is not particularly limited, but is preferably in the range of 1 minute to 5 hours, and more preferably in the range of 3 minutes to 1 hour. If the denaturation reaction time is too short, the reaction will not proceed sufficiently, and if the denaturation reaction time is too long, the polymer will easily gel.

The amount of conjugated diene polymer in the denaturing reaction solution is usually in the range of 2 to 300 g, preferably 10 to 200 g per liter of solvent.

The amount of the polymer modifier used in the modification reaction is usually 0.01 to 150 mmol, preferably 0.1 to 100 mmol, and more preferably 0.2 to 50 mmol with respect to 100 g of the conjugated diene polymer. In range. If the amount used is too small, the amount of the modifying group introduced into the modified conjugated diene polymer will be small, and a sufficient modification effect cannot be obtained. If the amount used is too large, the unreacted modifier remains in the modified conjugated diene polymer, and it takes time to remove the unreacted modifier, which is not preferable.

When carrying out the modification reaction, a modifier is added following the polymerization reaction, and then a polymerization inhibitor is added to remove the solvent and unreacted monomers remaining in the reaction product by steam stripping method, vacuum drying method, etc. Examples thereof include a method of removing with the above method, or a method of adding a polymer modifier after adding a polymerization terminator. Depending on the type of the polymerization terminator, the activity of the site where the polymer reacts with the polymer modifier may be reduced. Therefore, a method of adding the polymer modifier before the polymerization terminator is preferred is preferable.

^{It is confirmed by gel permeation chromatography (GPC) or 1} H-NMR that the conjugated diene polymer is modified by the polymer modifier of the present invention.
In particular, it is convenient to compare the magnitude of the UV / RI value obtained by GPC measurement of both the unmodified polymer and the modified polymer. The UV / RI value is the ratio of the peak area value UV obtained from the UV absorbance of the polymer in the GPC measurement and the peak area value RI obtained from the differential refractive index (RI).
In general, when the polymer is modified, UV absorption increases, so that the UV / RI value of the modified polymer is larger than that of the unmodified polymer.

<< Modified conjugated diene polymer >>
The modified conjugated diene polymer is obtained by the production method of the present invention, and has a structure derived from a compound represented by the following general formula (1) at the end of the conjugated diene polymer.

（Ｚは酸素原子又は硫黄原子を示す。
Ａ^１及びＡ^２は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す Ｒ^１及びＲ^２は、Ａ^１及びＡ^２の炭素原子と結合しており、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に０〜４の整数で、ｍ＋ｎ≧１を満たす数値である。）

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic ring group or a 6-membered ring aromatic heterocyclic group containing at least one nitrogen atom as a constituent element of the ring. R ¹ and R ² are carbons of ^{A 1} and A ^2. It is a saturated or unsaturated 3- to 12-membered ring heterocyclic group that is bonded to an atom and has an unsubstituted or substituent, respectively, and contains one nitrogen atom as a constituent element of the ring, and contains a nitrogen atom and oxygen. One heteroatom selected from the group consisting of an atom and a sulfur atom may be further contained as a constituent of the ring.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. )

Unless otherwise specified, the embodiment of the general formula (1) may be the same as that of the polymer modifier.

The "structure derived from the compound represented by the general formula (1)" indicates a partial structure other than the bonding group of the terminal of the conjugated diene polymer and the compound represented by the general formula (1). The structure derived from the compound represented by the general formula (1) is introduced into the terminal of the conjugated diene polymer by the compound represented by the general formula (1) to obtain a modified conjugated diene polymer.

More specifically, the "structure derived from the compound represented by the general formula (1)" is preferably the structure represented by the following general formulas (1'-1) and (1'-2).

（Ｃは炭素原子を示し、炭素原子は共役ジエン重合体の末端の炭素原子と結合している。
Ｒ^１及びＲ^２は、Ａ^１及びＡ^２の炭素原子と結合しており、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に０〜４の整数で、ｍ＋ｎ≧１を満たす数値である。）

(C represents a carbon atom, and the carbon atom is bonded to the carbon atom at the end of the conjugated diene polymer.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the ring, and one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the ring.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. )

The modified conjugated diene polymer preferably has a cis-1,4 structure of 94 mol% or more, and more preferably 95 mol% or more of cis-1,4-polybutadiene. The [η] of the modified conjugated diene polymer is preferably 0.1 to 10, more preferably 1 to 7, and even more preferably 1.5 to 5.

The number average molecular weight (Mn) of the modified conjugated diene polymer is preferably 1,000,000 to 1,000,000, more preferably 30,000 to 7,000, and even more preferably 50,000 to 550000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the modified conjugated diene polymer using the rare earth metal compound is preferably 1.5 to 10. It is more preferably ~ 7, and even more preferably 1.5-4. When Mw / Mn is within the above range, workability is excellent.

<< Modified conjugated diene polymer composition >>
The modified conjugated diene polymer composition according to the present embodiment (hereinafter, the modified conjugated diene polymer composition includes a rubber composition) contains one or more modified conjugated diene polymers of the present invention. It is preferable to include a modified conjugated diene polymer (α') according to the present invention, a diene-based polymer (β) other than (α'), and a rubber reinforcing agent (γ). In the method for producing a modified conjugated diene polymer composition according to the present embodiment, the conjugated diene compound is polymerized using the above-mentioned catalyst for conjugated diene polymerization, and the obtained conjugated diene polymer is further modified with a modifier to modify it. It is characterized by having a step of producing a conjugated diene polymer (α'). In other words, the method for producing a modified conjugated diene polymer composition according to the present embodiment includes a step of producing a modified conjugated diene polymer (α') by the method for producing a modified conjugated diene polymer of the present invention described above. It is characterized by that.

Specifically, the modified conjugated diene polymer of the present invention may be blended alone or blended with other synthetic or natural rubbers, vulcanized with process oil if necessary, and then a filler such as carbon black. , Vulcanization agent, vulcanization accelerator and other ordinary compounding agents are added to vulcanize, and the mechanical properties, wear resistance, etc. of tires, hoses, belts, crawler, and other various industrial products are required. It can be used for various purposes.

Further, the modified conjugated diene polymer of the present invention is used as a modifier for a plastic material, for example, impact-resistant polystyrene, that is, an impact-resistant polystyrene-based resin composition or a rubber-modified impact-resistant polystyrene-based resin composition. Can also be manufactured.

The mixing ratio of the modified conjugated diene polymer composition according to the present invention is preferably 90 to 5 parts by mass of the modified conjugated diene polymer (α') and 10 to 10 parts by mass of the diene polymer (β) other than (α'). It is 100 parts by mass of a rubber component (α') + (β) consisting of 95 parts by mass and 20 to 120 parts by mass of a rubber reinforcing agent (γ).

As the diene-based polymer (β) other than (α') contained in the modified conjugated diene polymer composition, vulverable rubber is preferable, and specifically, natural rubber (NR) and ethylene propylene diene rubber (EPDM). ), Nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), polyisoprene, high cis polybutadiene rubber, locis polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, bromine. Examples thereof include polymerized butyl rubber and acrylonitrile-butadiene rubber. Of these, NR and SBR are preferable. Further, in the case of SBR, solution-polymerized styrene-butadiene copolymer rubber (S-SBR) is particularly preferable, although it is not particularly limited. These rubbers may be used alone or in combination of two or more.

Examples of the rubber reinforcing agent (γ) used in the present invention include various inorganic reinforcing agents such as carbon black, silica, activated calcium carbonate, and ultrafine magnesium silicate. Of these, carbon black and silica are usually preferred. These rubber reinforcing agents may be used alone or in combination of two or more.

Examples of silica include silicon dioxide (represented by the general formula SiO ₂ ) and silicic acid-based fillers such as silicic anhydride, hydrous silicic acid, calcium silicate, and silicates such as aluminum silicate. Further, there are no particular restrictions on the aggregated state of silica such as dry silica, precipitation method silica, gel method silica, colloidal silica, and the production method such as wet method and dry method. These may be used alone or in combination of two or more. Wet silica having excellent wear resistance is preferable.

Further, a silane coupling agent can also be used as an additive. The silane coupling agent used as an additive is an organic silicon compound represented by ^{the general formula R 63} _n SiR ⁶⁴ _-n ^{, and R 63} is a vinyl group, an acyl group, an allyl group, an allyloxy group, an amino group or an epoxy group. , mercapto group, chloro group, alkyl group, phenyl group, hydrogen, a styryl group, a methacrylic group, an organic group having 1 to 20 carbon atoms having a reactive group selected from an acrylic group, a ureido group, R ⁶⁴ is chloro It is a hydrolyzing group selected from a group, an alkoxy group, an acetoxy group, an isopropenoxy group, an amino group and the like, and n represents an integer of 1 to 3. ^{As the R 63} of the above silane coupling agent, those containing a vinyl group and / or a chloro group are preferable.

The amount of the silane coupling agent added is preferably 0.2 to 20 parts by mass, more preferably 3 to 15 parts by mass, and particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the filler such as silica. .. If it is less than the above range, it may cause scorch. Further, if it is more than the above range, it may cause deterioration of tensile properties and elongation.

The modified conjugated diene polymer composition according to the present invention can be obtained by kneading each of the above components using a commonly used Banbury, open roll, kneader, biaxial kneader or the like.

The modified conjugated diene polymer composition according to the present invention is usually used in the rubber industry such as a vulcanizing agent, a vulcanization aid, an antioxidant, a filler, a process oil, zinc oxide, and stearic acid, if necessary. The compounding agent to be used may be kneaded.

As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide can be used. The vulcanizing agent is preferably blended in an amount of about 0.5 to 3 parts by mass with respect to 100 parts by mass of the rubber component (α) + (β) or (α') + (β).

As the vulcanization aid, known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates and the like can be used.

Examples of the antiaging agent include amine / ketone type, imidazole type, amine type, phenol type, sulfur type and phosphorus type.

Examples of the filler include inorganic fillers such as silica, calcium carbonate, basic magnesium carbonate, clay and diatomaceous earth, and organic fillers such as carbon black, recycled rubber and powdered rubber.

As the process oil, any of aromatic type, naphthenic type and paraffin type may be used.

The modified conjugated diene polymer composition obtained by the present invention is used for various rubber applications such as industrial products such as tires, anti-vibration rubbers, belts, hoses, and seismic isolation rubbers, and footwear such as men's shoes, women's shoes, and sports shoes. Can be used. In that case, it is preferable to blend the rubber component so as to contain at least 10% by weight of the modified conjugated diene polymer of the present invention. Further, the rubber-modified impact-resistant polystyrene-based resin composition can be used for various known molded products, but because of its excellent flame retardancy, impact resistance, and tensile strength, it is used in electrical / industrial applications, packaging materials, and housing. Suitable for related materials, materials for OA equipment, tools, daily necessities, etc. For example, it can be used in a wide range of applications such as housings for televisions, personal computers, air conditioners, exterior materials for office equipment such as copiers and printers, and food containers for frozen foods, lactic acid beverages, ice cream, and the like.

(Rubber composition for tires and rubber composition for rubber belts)
The above-mentioned modified conjugated diene polymer composition has a rubber composition for tires and a rubber composition for rubber belts by adjusting the mixing ratio of the rubber component (α') + (β) and the rubber reinforcing agent (γ), respectively. It can be suitably used as a product.

The tire of the present invention uses at least the above-mentioned modified conjugated diene polymer composition. The method for producing a tire according to the present embodiment is a method for producing a tire containing a modified conjugated diene polymer, which is obtained by polymerizing a conjugated diene compound using the above-mentioned catalyst for conjugated diene polymerization. Is further modified with a modifier to produce a modified conjugated diene polymer, in other words, a step of producing a modified conjugated diene polymer by the method for producing a modified conjugated diene polymer of the present invention described above. Is to be.

The rubber belt of the present invention uses at least the above-mentioned modified conjugated diene polymer composition. The method for producing a rubber belt according to the present embodiment is a method for producing a rubber belt containing a modified conjugated diene polymer, which is obtained by polymerizing a conjugated diene compound using the above-mentioned catalyst for conjugated diene polymerization. Is further modified with a modifier to produce a modified conjugated diene polymer, in other words, a step of producing a modified conjugated diene polymer by the method for producing a modified conjugated diene polymer of the present invention described above. Is to be.

In the case of a rubber composition for tires, the rubber composition is a rubber component composed of the modified conjugated diene polymer (α') of the present invention of the present invention and a diene polymer (β) other than (α'). It contains (α') + (β) and a rubber reinforcing agent (γ), and 30 to 80 parts by mass of the rubber reinforcing agent (γ) is added to 100 parts by mass of the rubber component (α') + (β). It is preferable to contain it.

Further, in the case of a rubber composition for a rubber belt, the rubber composition is a rubber component (β) composed of the modified conjugated diene polymer (α') of the present invention and a diene polymer (β) other than (α'). Contains α') + (β) and a rubber reinforcing agent (γ), and contains 20 to 70 parts by mass of the rubber reinforcing agent (γ) with respect to 100 parts by mass of the rubber component (α') + (β). It is preferable to do so.

The rubber composition for tires and the rubber composition for rubber belts according to the present invention contain a diene polymer (β) other than the modified conjugated diene polymer (α'), and the modified conjugated diene polymer (α') 90 to 5 It is preferable to add 10 to 95 parts by mass of a diene-based polymer (β) other than the modified conjugated diene polymer (α') with respect to parts by mass.
The diene-based polymer (β) blended in the rubber composition for tires and the rubber composition for rubber belts according to the present invention is at least one of natural rubber, styrene-butadiene rubber (SBR), and polyisoprene. Is preferable.

Examples of the rubber reinforcing agent (γ) blended in the rubber composition for tires and the rubber composition for rubber belts according to the present invention include various carbon blacks, silica, activated calcium carbonate, ultrafine magnesium silicate, talc, mica and the like. Can be mentioned. Above all, it is preferable that at least one of carbon black and silica is used.

The modified conjugated diene polymer of the present invention may be blended alone or blended with other synthetic or natural rubbers, oil-expanded with process oil if necessary, and then fillers such as carbon black, vulcanizers, and additions. Vulcanized by adding a vulcanization accelerator and other ordinary compounding agents, and used for rubber compositions that require mechanical properties, wear resistance and low fuel consumption such as tires, hoses, rubber belts and other various industrial products. Will be done. It can also be used as a modifier for plastic materials.

The present invention also includes the following inventions.
Bis (4- (1-methyl-1H-imidazol-2-yl) phenyl) methanone, bis (4- (1-phenyl-1H-imidazol-2-yl) phenyl) methanone, bis (4- (1-methyl) -1H-pyrazole-2-yl) phenyl) methanone, bis (4- (1H-imidazol-1-yl) phenyl) methanone, bis (4- (thiazole-2-yl) phenyl) methanone, bis (6- (6-( 1-Methyl-1H-imidazol-2-yl) Pyridine-3-yl) methanone, bis (4- (3- (diethylamino) pyrrolidine-1-yl) phenyl) methanone, bis (4- (4- (pyrridine-) 1-yl) piperidine-1-yl) phenyl) methanone, bis (4- (4- (trifluoromethyl) piperidine-1-yl) phenyl) methanone, bis (4-thiomorpholinophenyl) methanone, bis (4-yl) (1,4-Dioxa-8-azaspiro [4,5] decane-8-yl) phenyl) methanone, phenyl (4- (4-pyrridine-1-yl) piperidine-1-yl) phenyl) methanone, bis ( 4- (Thiazolidin-3-yl) phenyl) methanone, bis (4- (tetramethylpiperidine-1-l) phenyl) methanone, bis (6- (pyrrolidin-1-yl) pyridin-3-yl) methanone, bis (6- (3-diethylamino) pyrrolidine-1-yl) pyridin-3-yl) methanone, bis (6- (4- (pyrrolidin-1-yl) piperidine-1-yl) pyridin-3yl) methanone, bis (5- (Pyrrolidin-1-yl) pyridin-2-yl) methanone, bis (5- (3- (diethylaminopyrrolidin-1-yl) pyridin-2-yl) metanone and bis (5- (4- (pyrrolidin)) It is a compound selected from the group consisting of -1-yl) piperidine-1-yl) pyridin-2-yl) methanone.
In addition to the modifier for polymers, the compound is useful as a pharmaceutical product or an intermediate / active ingredient thereof, a luminescent material or an intermediate thereof, and the like.

（但し、Ｒ^６は炭素数１〜１２の少なくとも１つの窒素原子を含む炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは、１〜３の整数である。）
このような重合体用変性剤を用いて変性した変性共役ジエン重合体は、加工性、機械強度、耐摩耗性や低燃費性等の諸特性に優れたものとなる。<< Denaturer for polymer (2) >>
In addition, the present specification includes the following inventions.
That is, in the present specification, compounds represented by the following classifications (1) to (4) can be used as the modifier for the polymer.
[Category (1)]
The polymer modifier of classification (1) is characterized by containing a compound represented by the following general formula (1A).

(However, R ⁶ represents a hydrocarbon group containing at least one nitrogen atom having 1 to 12 carbon atoms, Z represents an oxygen atom or a sulfur atom, and m and n are integers of 1 to 3. )
The modified conjugated diene polymer modified by using such a modifier for a polymer is excellent in various properties such as processability, mechanical strength, abrasion resistance and fuel efficiency.

（但し、Ｒ^６は炭素数１〜１２の少なくとも１つの窒素原子を含む炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (2A), and more preferably a compound represented by the following general formula (3A).

(However, R ⁶ represents a hydrocarbon group containing at least one nitrogen atom having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^６は炭素数１〜１２の少なくとも１つの窒素原子を含む炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ⁶ represents a hydrocarbon group containing at least one nitrogen atom having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^６１は水素、または炭素数１〜１２の炭化水素基を表す。）Specific examples of R ⁶ in the general formula (1A) ~ (3A), dimethylamino group, methylethylamino group, diethylamino group, ethyl n- propylamino group, di-n- propylamino group, an ethyl isopropylamino group, diisopropylamino Examples thereof include amino groups such as an amino group, a pyrrolidino group, a piperidino group and a hexamethyleneimino group, and an imidazole-2-yl group represented by the following formula (4A).

(However, R ⁶¹ represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms.)

Examples of the hydrocarbon group having 1 to 12 carbon atoms in the formula (4A) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group and a t-butyl group. n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, heptyl group, Saturated hydrocarbon groups such as octyl, nonyl, decyl, undecyl and dodecyl groups, unsaturated hydrocarbon groups such as vinyl, 1-propenyl and allyl groups, cyclohexyl, methylcyclohexyl and ethyl Examples thereof include an alicyclic hydrocarbon group such as a cyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group, and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the above compounds include (4- (diethylamino) phenyl) (4- (trifluoromethyl) phenyl) methanone, 2- (diethylamino) phenyl) (4- (trifluoromethyl) phenyl) methanone, 3- (diethylamino). ) Phenyl) (4- (trifluoromethyl) phenyl) methanone, (3,4-bis (diethylamino) phenyl) (4- (trifluoromethyl) phenyl) methanone, (2,4-bis (diethylamino) phenyl) ( 4- (Trifluoromethyl) phenyl) methanone, (4- (diethylamino) phenyl) (2- (trifluoromethyl) phenyl) methanone, 4- (diethylamino) phenyl) (3- (trifluoromethyl) phenyl) methanone, (4- (Diethylamino) phenyl) (2,4-bis (trifluoromethyl) phenyl) methanone, (4- (diethylamino) phenyl) (3,4-bis (trifluoromethyl) phenyl) methanone, (2,4 -Bis (diethylamino) phenyl) (2,4-bis (trifluoromethyl) phenyl) methanone, (3,4-bis (diethylamino) phenyl) (3,4-bis (trifluoromethyl) phenyl) methanone, (4 -(1-Methyl-1H-imidazol-2-yl) phenyl) (4- (trifluoromethyl) phenyl) methanone, (2- (1-methyl-1H-imidazol-2-yl) phenyl) (4-( Trifluoromethyl) phenyl) methanone, (3- (1-methyl-1H-imidazol-2-yl) phenyl) (4- (trifluoromethyl) phenyl) methanone, (4- (1-methyl-1H-imidazole-) 2-yl) phenyl) (2- (trifluoromethyl) phenyl) methanone, (4- (1-methyl-1H-imidazol-2-yl) phenyl) (3- (trifluoromethyl) phenyl) methanone, etc. However, (4- (diethylamino) phenyl) (4- (trifluoromethyl) phenyl) methanone, (4- (1-methyl-1H-imidazol-2-yl) phenyl) (4- (trifluoromethyl) phenyl) ) Metanon is preferred.
It is possible to obtain a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone or in combination of two or more.

The modifiers for polymers in this category include raw material (A) a halide benzene compound having a trifluoromethyl group, raw material (B) a benzonitrile compound substituted with a nitrogen-containing functional group, and raw material (C) Periodic Table No. 1. It is preferably synthesized from an organic metal compound of an element selected from Group 2, Group 2, and Group 12 and a halide thereof.

As the raw material (A), 1-bromo-4-trifluoromethylbenzene, 1-chloro-4-trifluoromethylbenzene, 1-iodo-4-trifluoromethylbenzene, 2-bromo-4-trifluoromethylbenzene , 2-Chloro-4-trifluoromethylbenzene, 2-iodo-4-trifluoromethylbenzene and the like.

As the raw material (B), 4-diisopropylaminobenzonitrile, 4-dimethylaminobenzonitrile, 4-diisopropylaminobenzonitrile, 3-diethylaminobenzonitrile, 3-dimethylaminobenzonitrile, 3-diisopropylaminobenzonitrile, 4-( 1-Methylimidazol-2-yl) benzonitrile and the like can be mentioned.

Examples of the raw material (C) include n-butyllithium, sec-butyllithium, tert-butyllithium, n-butylmagnesium chloride and the like.

The synthetic reaction of the modifiers for polymers of this category may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not easily inhibit the reaction. For example, benzene, toluene, xylene, etc. Aromatic hydrocarbons such as ethylbenzene and cumene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, cyclopentane and cyclohexane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran can be mentioned. However, ethers are preferably used. These solvents may be used alone or in combination of two or more.

If necessary, the synthesis reaction of the polymer modifiers of this classification may be carried out in the presence of a metal complex catalyst such as palladium.

The reaction temperature in this classification is -100 to 100 ° C, preferably -80 to 60 ° C.

The polymer modifiers of this category are separated and purified by general methods such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｘ及びＹは、窒素原子を含む不飽和環状構造を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような重合体用変性剤を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。
前記一般式（１Ｂ）で表される化合物は、下記小分類（Ａ）〜（Ｇ）で表される化合物であることが好ましい。
以下、各分類について詳細に説明する。[Category (2)]
The polymer modifier of classification (2) is characterized by containing a compound represented by the following general formula (1B).

(However, X and Y represent an unsaturated cyclic structure containing a nitrogen atom, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a modifier for a polymer is excellent in various properties such as processability, wear resistance and fuel efficiency.
The compound represented by the general formula (1B) is preferably a compound represented by the following subclasses (A) to (G).
Hereinafter, each classification will be described in detail.

（但し、Ｒ^７及びＲ^８は炭素数１〜１２の炭化水素基を表し、Ｒ^９、Ｒ^１０、Ｒ^１１及びＲ^１２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。(Small classification (A))
The compound is preferably a compound represented by the following general formula (2aB).

(However, R ⁷ and R ⁸ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Z represents a hydrocarbon group having 1 to 12 carbon atoms. Represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^７及びＲ^８は炭素数１〜１２の炭化水素基を表し、Ｒ^９、Ｒ^１０、Ｒ^１１及びＲ^１２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (2bB), more preferably a compound represented by the following general formula (2cB), and is represented by the following general formula (2dB). It is more preferable that the compound is a compound.

(However, R ⁷ and R ⁸ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Z represents a hydrocarbon group having 1 to 12 carbon atoms. Represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^７及びＲ^８は炭素数１〜１２の炭化水素基を表し、Ｒ^９、Ｒ^１０、Ｒ^１１及びＲ^１２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ⁷ and R ⁸ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Z represents a hydrocarbon group having 1 to 12 carbon atoms. Represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^７及びＲ^８は炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ⁷ and R ⁸ represent hydrocarbon groups having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of the subclass (A) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an s-butyl group. , Isobutyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethyl Saturated hydrocarbon groups such as propyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, unsaturated hydrocarbon groups such as vinyl, 1-propenyl, and allyl groups, Examples thereof include an alicyclic hydrocarbon group such as a cyclohexyl group, a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (A) include bis (4- (1-methyl-1H-imidazol-2-yl) phenyl) methanone and bis (4- (1-ethyl-1H-imidazol-2-yl) -2-. Phenyl) methanone, bis (4- (1-isopropyl-1H-imidazol-2-yl) phenyl) methanone, bis (4- (1-phenyl-1H-imidazol-2-yl) phenyl) methanone, bis ( Examples thereof include 4- (1-2,6-diisopropylphenyl-1H-imidazol-2-yl) phenyl) methanone, but bis (4- (1-methyl-1H-imidazol-2-yl) phenyl) methanone, Bis (4- (1-phenyl-1H-imidazol-2-yl) phenyl) methanone is preferred.
It is possible to obtain a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone, in combination of a plurality of types, or in combination with the compounds of the subclasses (B) to (G) described later.

The compound belonging to the subclass (A) is an element selected from the raw material (A) halogenated benzophenone compound, the raw material (B) imidazolium compound, and the raw material (C) Group 1, Group 2, and Group 12 of the periodic table. It is preferably synthesized from an organic metal compound, a halide thereof, an organic metal compound of an element selected from Group 10 and Group 11 of the periodic table (D), and a coordinating compound.

As the raw material (A), 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3, 3'-diiodobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3' , 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include 1-methylimidazole, 1-ethylimidazole, 1-isopropyl imidazole, 1-phenylimidazole, 1- (2,6-diisopropylphenyl) imidazole and the like.

Examples of the raw material (C) include n-butyllithium, sec-butyllithium, tert-butyllithium, zinc chloride and the like.

As the catalyst component (D), copper acetate, copper 2-thiophene carboxylate, nickel chloride, bis (1,5-cycloteoctadiene) nickel, palladium acetate, bis (dibenzilidenacetone) palladium, tetrakistriphenylphosphine palladium, Examples thereof include bipyridine, 1,10-phenanthroline, triphenylphosphine, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2- (dicyclohexylphosphino) biphenyl and the like.

The synthetic reaction of the compound belonging to the subclass (A) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is difficult to inhibit the reaction, and for example, benzene, toluene and xylene. , Ethylbenzene, Cumene and other aromatic hydrocarbons; n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane and other aliphatic hydrocarbons; diethyl ether, diisopropyl ether, tetrahydrofuran and other ethers. However, ethers are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of the above synthetic reaction is -100 to 100 ° C, preferably -80 to 30 ° C.

（但し、Ｒ^１３及びＲ^１４は炭素数１〜１２の炭化水素基を表し、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。The compound belonging to the subclass (A) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.
(Small classification (B))
The compound is preferably a compound represented by the following general formula (3aB).

(However, R ¹³ and R ¹⁴ represent hydrocarbon groups having 1 to 12 carbon atoms, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Z represents a hydrocarbon group having 1 to 12 carbon atoms. Represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^１３及びＲ^１４は炭素数１〜１２の炭化水素基を表し、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (3bB), more preferably a compound represented by the following general formula (3cB), and is represented by the following general formula (3dB). It is more preferable that the compound is a compound.

(However, R ¹³ and R ¹⁴ represent hydrocarbon groups having 1 to 12 carbon atoms, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Z represents a hydrocarbon group having 1 to 12 carbon atoms. Represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^１３及びＲ^１４は炭素数１〜１２の炭化水素基を表し、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ¹³ and R ¹⁴ represent hydrocarbon groups having 1 to 12 carbon atoms, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Z represents a hydrocarbon group having 1 to 12 carbon atoms. Represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^１３及びＲ^１４は炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ¹³ and R ¹⁴ represent hydrocarbon groups having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of this subclass include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group and isobutyl. Group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group , Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group. , Alicyclic hydrocarbon groups such as methylcyclohexyl group and ethylcyclohexyl group, and aromatic hydrocarbon groups such as phenyl group, benzyl group, toluyl group and phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (B) include bis (4- (1-methyl-1H-pyrazol-2-yl) phenyl) methanone and bis (4- (1-ethyl-1H-pyrazol-2-yl) -2-pyrazole-2-. Phenyl) methanone, bis (4- (1-isopropyl-1H-pyrazol-2-yl) phenyl) methanone, bis (4- (1-phenyl-1H-pyrazole-2-yl) phenyl) methanone, etc. However, bis (4- (1-methyl-1H-pyrazol-2-yl) phenyl) methanone is preferred.
It is possible to obtain a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone, in combination of a plurality of types, or in combination of the compounds of the subclasses (A) and (C) to (G).

The compound belonging to the subclass (B) is an organic element selected from the raw material (A) halogenated benzophenone compound, the raw material (B) pyrazole compound, and the raw material (C) Periodic Table Group 1, Group 2, and Group 12. It is preferably synthesized from a metal compound, a halide thereof, an organic metal compound of an element selected from Group 10 and Group 11 of the periodic table (D), and a coordinating compound.

As the raw material (A), 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3, 3'-diiodobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3' , 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include 1-pyrazole, 1-ethylpyrazole, 1-isopropylpyrazole, 1-phenylpyrazole and the like.

Examples of the raw material (C) include n-butyllithium, sec-butyllithium, tert-butyllithium, zinc chloride and the like.

As the catalyst component (D), copper acetate, copper 2-thiophene carboxylate, nickel chloride, bis (1,5-cycloteoctadiene) nickel, palladium acetate, bis (dibenzilidenacetone) palladium, tetrakistriphenylphosphine palladium, Examples thereof include bipyridine, 1,10-phenanthroline, triphenylphosphine, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2- (dicyclohexylphosphino) biphenyl and the like.

The synthetic reaction of the compound belonging to the subclass (B) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is difficult to inhibit the reaction, and for example, benzene, toluene and xylene. , Ethylbenzene, Cumene and other aromatic hydrocarbons; n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane and other aliphatic hydrocarbons; diethyl ether, diisopropyl ether, tetrahydrofuran and other ethers. However, ethers are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 100 ° C, preferably -80 to 30 ° C.

The compound belonging to the subclass (B) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^１９〜Ｒ^２６は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。(Small classification (C))
The compound is preferably a compound represented by the following general formula (4aB).

(However, R ^{19 to} R ²⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^１９〜Ｒ^２６は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (4bB), more preferably a compound represented by the following general formula (4cB), and is represented by the following general formula (4dB). It is more preferable that the compound is a compound.

(However, R ^{19 to} R ²⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^１９〜Ｒ^２６は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ^{19 to} R ²⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｚは酸素原子または硫黄原子を表す。）

(However, Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of this subclass include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group and isobutyl. Group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group , Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group. , Alicyclic hydrocarbon groups such as methylcyclohexyl group and ethylcyclohexyl group, and aromatic hydrocarbon groups such as phenyl group, benzyl group, toluyl group and phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (C) include bis (4- (1H-pyrrole-1-yl) phenyl) methanone and bis (4- (3-methyl-1H-pyrrole-1-yl) phenyl). Metanon, bis (4- (3-heptyl-1H-pyrrole-1-yl) phenyl) methanone, bis (4- (2-ethyl-1H-pyrrole-1-yl) phenyl) methanone, bis (4- ( Examples thereof include 2,4-dimethyl-1H-pyrrole-1-yl) phenyl) methanone and bis (4- (2,5-dimethyl-1H-pyrrole-1-yl) phenyl) methanone. (1H-pyrrole-1-yl) phenyl) methanone is preferred.
It is possible to obtain a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone, a plurality of types may be used in combination, or compounds of the subclasses (A), (B) and (D) to (G) may be used in combination.

The compound belonging to the subclass (C) is preferably synthesized by the raw material (A) halogenated benzophenone compound, the raw material (B) pyrrole compound, and the raw material (C) Group 1 of the periodic table.

As the raw material (A), 2,2'-difluorobenzophenone, 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-difluorobenzophenone, 3, 3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4 Examples thereof include'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3', 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include pyrrole, 3-methylpyrrole, 3-heptylpyrrole, 2-ethylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole and the like.

Examples of the raw material (C) include sodium carbonate, cesium carbonate, tripotassium phosphate and the like.

The synthetic reaction of the compound belonging to the subclass (C) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is a solvent that does not easily inhibit the reaction. Aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; n-pentane, n-hexane, n-heptane, cyclo Aliphatic hydrocarbons such as pentane and cyclohexane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran can be mentioned, but aprotic polar solvents are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 150 ° C, preferably 0 to 120 ° C.
The compound belonging to the subclass (C) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^２７〜Ｒ^３２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。(Small classification (D))
The compound is preferably a compound represented by the following general formula (5aB).

(However, R ^{27 to} R ³² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^２７〜Ｒ^３２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (5bB), more preferably a compound represented by the following general formula (5cB), and is represented by the following general formula (5dB). It is more preferable that the compound is a compound.

(However, R ^{27 to} R ³² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^２７〜Ｒ^３２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ^{27 to} R ³² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｚは酸素原子または硫黄原子を表す。）

(However, Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of this classification include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group and an isobutyl group. , T-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group, Examples thereof include an alicyclic hydrocarbon group such as a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (D) include bis (4- (1H-imidazol-1-yl) phenyl) methanone and bis (4- (2-methyl-1H-imidazol-1-yl) phenyl). Metanon, bis (4- (2-isopropyl-1H-imidazol-1-yl) phenyl) methanone, bis (4- (2-phenyl-1H-imidazol-1-yl) phenyl) methanone, bis (4- (4) -Methyl-1H-imidazol-1-yl) phenyl) methanone, bis (4- (4-phenyl-1H-imidazol-1-yl) phenyl) methanone, bis (4- (5-ethyl-1H-imidazol-1) -Il) phenyl) methanone and the like can be mentioned, but bis (4- (1H-imidazol-1-yl) phenyl) methanone is preferable.
It is possible to obtain a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone, a plurality of types may be used in combination, or compounds of the subclasses (A) to (C) and (E) to (G) may be used in combination.

The compound belonging to the subclass (D) is synthesized from a raw material (A) halogenated benzophenone compound, a raw material (B) imidazole compound, and a raw material (C) an organometallic compound of an element selected from Group 1 of the periodic table. Is preferable.

As the raw material (A), 2,2'-difluorobenzophenone, 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-difluorobenzophenone, 3, 3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4 Examples thereof include'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3', 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include imidazole, 2-methylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 4-methylimidazole, 4-phenylimidazole, 5-ethylimidazole and the like.

Examples of the raw material (C) include sodium carbonate, cesium carbonate, tripotassium phosphate and the like.

The synthetic reaction of the compound belonging to the subclass (D) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is a solvent that does not easily inhibit the reaction. Aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; n-pentane, n-hexane, n-heptane, cyclo Aliphatic hydrocarbons such as pentane and cyclohexane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran can be mentioned, but aprotic polar solvents are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 150 ° C, preferably 0 to 120 ° C.
The compound belonging to the subclass (D) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^３３〜Ｒ^４４は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。(Small classification (E))
The compound is preferably a compound represented by the following general formula (6aB).

(However, R ^{33 to} R ⁴⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^３３〜Ｒ^４４は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (6bB), more preferably a compound represented by the following general formula (6cB), and is represented by the following general formula (6dB). It is more preferable that the compound is a compound.

(However, R ^{33 to} R ⁴⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^３３〜Ｒ^４４は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ^{33 to} R ⁴⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｚは酸素原子または硫黄原子を表す。）

(However, Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of this classification include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group and an isobutyl group. , T-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group, Examples thereof include an alicyclic hydrocarbon group such as a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (E) include bis (4- (1H-pyroline-2-yl) phenyl) methanone.

The compound belonging to the subclass (E) is synthesized by an organometallic compound of an element selected from the raw material (A) halogenated benzophenone compound, the raw material (B) pyrroline compound, and the raw material (C) Group 1 of the periodic table. Is preferable.

As the raw material (A), 2,2'-difluorobenzophenone, 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-difluorobenzophenone, 3, 3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4 Examples thereof include'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3', 5,5'-tetrabromobenzophenone and the like.
Further, the compound may be used alone, a plurality of types may be used in combination, or compounds of the subclasses (A) to (D), (F) and (G) may be used in combination.

Examples of the raw material (B) include pyrroline and pyrroline hydrochloride.

Examples of the raw material (C) include sodium carbonate, cesium carbonate, tripotassium phosphate and the like.

The synthetic reaction of the compound belonging to the subclass (E) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is a solvent that does not easily inhibit the reaction. Aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; n-pentane, n-hexane, n-heptane, cyclo Aliphatic hydrocarbons such as pentane and cyclohexane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran can be mentioned, but aprotic polar solvents are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 150 ° C, preferably 0 to 120 ° C.
The compound belonging to the subclass (E) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^４５〜Ｒ^５２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。(Small classification (F))
The compound is preferably a compound represented by the following general formula (7aB).

(However, R ^{45 to} R ⁵² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^４５〜Ｒ^５２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (7bB), more preferably a compound represented by the following general formula (7cB), and is represented by the following general formula (7dB). It is more preferable that the compound is a compound.

(However, R ^{45 to} R ⁵² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^４５〜Ｒ^５２は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ^{45 to} R ⁵² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｚは酸素原子または硫黄原子を表す。）

(However, Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of this classification include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group and an isobutyl group. , T-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group, Examples thereof include an alicyclic hydrocarbon group such as a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (F) include bis (4- (1-indolin-1-yl) phenyl) methanone and bis (4- (2-methylindoline-1-yl) phenyl) methanone. Although mentioned, bis (4- (1-indoline-1-yl) phenyl) methanone is preferable.
As a result, a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency can be obtained.
Further, the compound may be used alone, in combination of a plurality of types, or in combination of the compounds of the subclasses (A) to (E) and (G).

The compound belonging to the subclass (F) is synthesized from a raw material (A) halogenated benzophenone compound, a raw material (B) indolin compound, and a raw material (C) an organometallic compound of an element selected from Group 1 of the periodic table. Is preferable.

As the raw material (A), 2,2'-difluorobenzophenone, 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-difluorobenzophenone, 3, 3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4 Examples thereof include'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3', 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include indoline and 2-methylindoline.

Examples of the raw material (C) include sodium carbonate, cesium carbonate, tripotassium phosphate and the like.

The synthetic reaction of the compound belonging to the subclass (F) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is a solvent that does not easily inhibit the reaction. Aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; n-pentane, n-hexane, n-heptane, cyclo Aliphatic hydrocarbons such as pentane and cyclohexane; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran can be mentioned, but aprotic polar solvents are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 150 ° C, preferably 0 to 120 ° C.

The compound belonging to the subclass (F) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^５３〜Ｒ^５６は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは１〜３の整数である。）
このような化合物を用いて変性した変性共役ジエン重合体は、加工性、耐摩耗性や低燃費性等の諸特性に優れたものとなる。(Small classification (G))
The compound is preferably a compound represented by the following general formula (8aB).

(However, R ^{53 to} R ⁵⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a compound is excellent in various properties such as processability, wear resistance and fuel efficiency.

（但し、Ｒ^５３〜Ｒ^５６は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (8bB), more preferably a compound represented by the following general formula (8cB), and is represented by the following general formula (8dB). It is more preferable that the compound is a compound.

(However, R ^{53 to} R ⁵⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^５３〜Ｒ^５６は水素原子あるいは炭素数１〜１２の炭化水素基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ^{53 to} R ⁵⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｚは酸素原子または硫黄原子を表す。）

(However, Z represents an oxygen atom or a sulfur atom.)

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms in each general formula of this classification include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group and an isobutyl group. , T-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group, Examples thereof include an alicyclic hydrocarbon group such as a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

Specific examples of the compound belonging to the subclass (G) include bis (4- (thiazole-2-yl) phenyl) methanone, bis (4- (4-methyl-thiazole-2-yl) phenyl) methanone, and bis ( Examples thereof include 4- (5-methyl-thiazole-2-yl) phenyl) methanone and bis (4- (4,5-dimethyl-thiazole-2-yl) phenyl) methanone, and bis (4- (thiazole-) bis (thiazole-). 2-Il) phenyl) metanone is preferred.
It is possible to obtain a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency.
Further, the compound may be used alone, a plurality of types may be used in combination, or compounds of the subclasses (A) to (F) may be used in combination.

The compound belonging to the subclass (G) is an organic element selected from the raw material (A) halogenated benzophenone compound, the raw material (B) thiazole compound, and the raw material (C) Group 1, Group 2, and Group 12 of the periodic table. It is preferably synthesized from a metal compound, a halide thereof, an organic metal compound of an element selected from Group 10 and Group 11 of the periodic table (D), and a coordinating compound.

As the raw material (A), 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3, 3'-diiodobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3' , 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include thiazole, 4-methylthiazole, 5-methylthiazole, 4,5-dimethylthiazole and the like.

Examples of the raw material (C) include n-butyllithium, sec-butyllithium, tert-butyllithium, zinc chloride and the like.

As the catalyst component (D), copper acetate, copper 2-thiophene carboxylate, nickel chloride, bis (1,5-cycloteoctadiene) nickel, palladium acetate, bis (dibenzilidenacetone) palladium, tetrakistriphenylphosphine palladium, Examples thereof include bipyridine, 1,10-phenanthroline, triphenylphosphine, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2- (dicyclohexylphosphino) biphenyl and the like.

The synthetic reaction of the compound belonging to the subclass (G) may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is difficult to inhibit the reaction, and for example, benzene, toluene and xylene. , Ethylbenzene, Cumene and other aromatic hydrocarbons; n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane and other aliphatic hydrocarbons; diethyl ether, diisopropyl ether, tetrahydrofuran and other ethers. However, ethers are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of the synthetic reaction of this classification is -100 to 100 ° C, preferably -80 to 30 ° C.
The compound belonging to the subclass (G) is separated and purified by a general method such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^５７及びＲ^５８は窒素原子を４個以下含む炭素数２〜１４の不飽和環状構造を有する基を表し、Ｎは窒素原子、Ｚは酸素原子または硫黄原子を表す。なお、ｍは１〜４、ｎは１〜４の整数である。）
このような重合体用変性剤を用いて変性した変性共役ジエン重合体は、加工性、機械強度、耐摩耗性や低燃費性等の諸特性に優れたものとなる。[Category (3)]
The polymer modifier of this classification is characterized by containing a compound represented by the following general formula (1C).

(However, R ⁵⁷ and R ⁵⁸ represent a group having an unsaturated cyclic structure having 2 to 14 carbon atoms containing 4 or less nitrogen atoms, N represents a nitrogen atom, and Z represents an oxygen atom or a sulfur atom. Is an integer of 1 to 4, and n is an integer of 1 to 4.)
The modified conjugated diene polymer modified by using such a modifier for a polymer is excellent in various properties such as processability, mechanical strength, abrasion resistance and fuel efficiency.

（但し、Ｒ^５７及びＲ^５８は窒素原子を４個以下含む炭素数２〜１４の不飽和環状構造を有する基を表し、Ｎは窒素原子、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (2C), and more preferably a compound represented by the following general formula (3C).

(However, R ⁵⁷ and R ⁵⁸ represent a group having an unsaturated cyclic structure having 2 to 14 carbon atoms containing 4 or less nitrogen atoms, N represents a nitrogen atom, and Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^５７及びＲ^５８は窒素原子を４個以下含む炭素数２〜１４の不飽和環状構造を有する基を表し、Ｎは窒素原子、Ｚは酸素原子または硫黄原子を表す。）

(However, R ⁵⁷ and R ⁵⁸ represent a group having an unsaturated cyclic structure having 2 to 14 carbon atoms containing 4 or less nitrogen atoms, N represents a nitrogen atom, and Z represents an oxygen atom or a sulfur atom.)

Specifically, as R ⁵⁷ and R ⁵⁸ , an aromatic amino group such as a phenylamino group or a diphenylamino group, or a hydrogen such as a pyridine-2-ylamino group or a bis (pyridin-2-yl) amino group is a heterocycle. Examples thereof include a heterocyclic amino group such as an amino group substituted with, a pyridyl group, a pyrrole group, an imidazole group, and a pyrazole group, or a group in which the hydrogen of these groups is substituted with a hydrocarbon group.

Specific examples of the compound include bis (6- (methyl (phenyl) amino) pyridin-3-yl) methanone, bis (6- (methyl (pyridine-2-yl) amino) pyridin-3-yl) methanone, and bis. Examples thereof include (6- (di (pyridin-2-yl) amino) pyridin-3-yl) methanone and bis (6- (1-methyl-1H-imidazol-2-yl) pyridin-3-yl) metanone. However, bis (6- (methyl (phenyl) amino) pyridin-3-yl) methanone, bis (6- (1-methyl-1H-imidazol-2-yl) pyridin-3-yl) methanone, bis (6-yl) (Methyl (pyridin-2-yl) amino) pyridin-3-yl) methanone is preferred.
As a result, a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency can be obtained.
Further, the compound may be used alone or in combination of two or more.

The modifiers for polymers in this category are raw material (A) dihalogenated pyridine compound, raw material (B) halogenated pyridine carboxylaldehyde compound, raw material (C) imidazolium compound, raw material (D) Group 1 of the Periodic Table of the Period, No. 1 Synthesized from organic metal compounds of elements selected from Group 2 and Group 12 and their halides, organic metal compounds of elements selected from Group 10 and Group 11 of the Periodic Table of the Periodic Table (E), and coordinating compounds. Is preferable.

Examples of the raw material (A) include 3-bromo-5-iodopyridine, 3-fluoro-5-chloropyridine, 3-fluoro-5-bromopyridine, 3-fluoro-5-iodopyridine, and the like.

Raw materials (B) 6-bromo-3-pyridinecarboxyaldehyde, 6-fluoro-3-pyridinecarboxyaldehyde, 6-chloro-3-pyridinecarboxyaldehyde, 6-iodo-3-pyridinecarboxyaldehyde, and the like can be mentioned.

Examples of the raw material (C) include 1-methylimidazole, 1-ethylimidazole, 1-isopropyl imidazole, 1-phenylimidazole, 1- (2,6-diisopropylphenyl) imidazole and the like.

As the raw material (D), n-butyllithium, sec-butyllithium, tert-butyllithium, n-butylmagnesium chloride, isopropylmagnesium chloride, sodium ethoxydo, sodium tert-butoxide, potassium tert-butoxide, potassium peroxymonosulfate. , Potassium permanganate, Potassium-2-iodo-5-methylbenzenesulfonate, zinc chloride, and the like.

The catalyst component (E) includes copper acetate, copper 2-thiophene carboxylate, nickel chloride, bis (1,5-cycloteoctadiene) nickel, palladium acetate, bis (dibenzilidenacetone) palladium, and tetrakistriphenylphosphine palladium. , Bipyridine, 1,10-phenanthroline, triphenylphosphine, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2- (dicyclohexylphosphino) biphenyl and the like.

The synthetic reaction of the modifiers for polymers of this category may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not easily inhibit the reaction. For example, benzene, toluene, xylene, etc. Aromatic hydrocarbons such as ethylbenzene and cumene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, cyclopentane and cyclohexane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane Although it can be mentioned, ethers are preferably used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 100 ° C, preferably -80 to 70 ° C.

The polymer modifiers of this category are separated and purified by general methods such as crystallization, recrystallization, distillation, column chromatography and the like.

（但し、Ｒ^５９及びＲ^６０は炭素数１〜１２の炭化水素基を表し、Ａｒ^１及びＡｒ^２は、窒素原子を０〜４個含む炭素数４〜１４の不飽和環状構造を有する基を表し、Ｚは酸素原子または硫黄原子を表す。なお、ｍ及びｎは、１〜３の整数である。）
このような重合体用変性剤を用いて変性した変性共役ジエン重合体は、加工性、機械強度、耐摩耗性や低燃費性等の諸特性に優れたものとなる。[Category (4)]
The polymer modifier of the present invention is characterized by containing a compound represented by the following general formula (1D).

(However, R ⁵⁹ and R ⁶⁰ represent hydrocarbon groups having 1 to 12 carbon atoms, and Ar ¹ and Ar ² have groups having an unsaturated cyclic structure having 4 to 14 carbon atoms containing 0 to 4 nitrogen atoms. Representing, Z represents an oxygen atom or a sulfur atom. M and n are integers of 1 to 3).
The modified conjugated diene polymer modified by using such a modifier for a polymer is excellent in various properties such as processability, mechanical strength, abrasion resistance and fuel efficiency.

（但し、Ｒ^５９及びＲ^６０は炭素数１〜１２の炭化水素基を表し、Ａｒ^１及びＡｒ^２は、窒素原子を０〜４個含む炭素数４〜１４の不飽和環状構造を有する基を表し、Ｚは酸素原子または硫黄原子を表す。）Further, the compound is preferably a compound represented by the following general formula (2D), and more preferably a compound represented by the following general formula (3D).

(However, R ⁵⁹ and R ⁶⁰ represent hydrocarbon groups having 1 to 12 carbon atoms, and Ar ¹ and Ar ² have groups having an unsaturated cyclic structure having 4 to 14 carbon atoms containing 0 to 4 nitrogen atoms. Represents, Z represents an oxygen atom or a sulfur atom.)

（但し、Ｒ^５９及びＲ^６０は炭素数１〜１２の炭化水素基を表し、Ａｒ^１及びＡｒ^２は、窒素原子を０〜４個含む炭素数４〜１４の不飽和環状構造を有する基を表し、Ｚは酸素原子または硫黄原子を表す。）

(However, R ⁵⁹ and R ⁶⁰ represent hydrocarbon groups having 1 to 12 carbon atoms, and Ar ¹ and Ar ² have groups having an unsaturated cyclic structure having 4 to 14 carbon atoms containing 0 to 4 nitrogen atoms. Represents, Z represents an oxygen atom or a sulfur atom.)

Specific examples of Ar ¹ and Ar ² include a phenyl group, a naphthyl group, a heterocyclic amino group (pyridyl group, pyrrole group, etc.), or the hydrogen of these groups is substituted with a hydrocarbon group or an amino group. The group can be mentioned.

Specific examples of the compound include bis (4- (methyl (phenyl) amino) phenyl) methanone, bis (4- (methyl (pyridine-2-yl) amino) phenyl) methanone, and bis (4- (ethyl (phenyl)). Amino) phenyl) methanone, bis (4- (isopropyl (phenyl) amino) phenyl) methanone, bis (4- (methyl (naphthyl) amino) phenyl) methanone, bis (4- (methyl (pyridyl) amino) phenyl) methanone , Bis (4- (ethyl (pyridyl) amino) phenyl) methanone, etc., but bis (4- (methyl (phenyl) amino) phenyl) methanone, bis (4- (methyl (pyridine-2-yl) amino) ) Phenyl) methanone is preferred.
As a result, a modified conjugated diene polymer having excellent various properties such as workability, mechanical strength, wear resistance and fuel efficiency can be obtained.
Further, the compound may be used alone or in combination of two or more.

The modifiers for polymers in this category include raw materials (A) halogenated benzophenone compounds, raw materials (B) aromatic secondary amines, raw materials (C) organic metal compounds of elements selected from Group 1 of the periodic table, and catalysts. Component (D) It is preferable that the compound is synthesized from an organic metal compound and a coordinating compound of an element selected from Group 10 and Group 11 of the periodic table.

As the raw material (A), 2,2'-difluorobenzophenone, 2,2'-dichlorobenzophenone, 2,2'-dibromobenzophenone, 2,2'-diiodobenzophenone, 3,3'-difluorobenzophenone, 3, 3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4 Examples thereof include'-diiodobenzophenone, 2,2', 4,4'-tetrabromobenzophenone, 3,3', 5,5'-tetrabromobenzophenone and the like.

Examples of the raw material (B) include N-methylaniline, N-ethylaniline, N-isopropylaniline, N-methyl-1-naphthylamine, 2- (methylamino) pyridine, 2- (ethylamino) pyridine and the like.

Examples of the raw material (C) include sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide and the like.

As the catalyst component (D), copper acetate, copper 2-thiophene carboxylate, nickel chloride, bis (1,5-cycloteoctadiene) nickel, palladium acetate, bis (dibenzilidenacetone) palladium, tetrakistriphenylphosphine palladium, Examples thereof include bipyridine, 1,10-phenanthroline, triphenylphosphine, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2- (dicyclohexylphosphine) biphenyl and the like.

The synthetic reaction of the modifiers for polymers of this category may be carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it is a solvent that does not easily inhibit the reaction. For example, benzene, toluene, xylene, etc. Aromatic hydrocarbons such as ethylbenzene and cumene; non-polar proton solvents such as N, N-dimethylformamide, dimethylsulfoxide and dimethylacetamide; ethers such as dioxane and 2-methyltetraxamine are preferable. Hydrocarbons are used. These solvents may be used alone or in combination of two or more.

The reaction temperature of this classification is -100 to 100 ° C, preferably -80 to 30 ° C.
The polymer modifiers of this category are separated and purified by general methods such as crystallization, recrystallization, distillation, column chromatography and the like.

Regarding the method for producing a modified conjugated diene polymer using << polymer modifier (2) >> belonging to each of the above categories, the modified conjugated diene polymer and the modified conjugated diene polymer composition, the above-mentioned << polymer The contents are the same as those described in the columns of "Method for producing modified conjugated diene polymer", "Modified conjugated diene polymer" and "Modified conjugated diene polymer composition" in "Modifying agent for use (1)". Is omitted.
Further, the modified conjugated diene polymers obtained by the method for producing a modified conjugated diene polymer using a polymer modifier belonging to each of the above categories are described in the columns of the above categories at the ends of the conjugated diene polymers. It has a structure derived from the compound represented by each of the above general formulas.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

1-1. Polymer modifiers (1) "( ^{Compounds in which A 1} and A ^{2 in} formula (1) are 6-membered ring aromatic ring groups and R ¹ and R ² are saturated 3- to 12-membered ring heterocyclic groups) Synthesis example of "Synthesis example" The synthesis example of the modifier for polymer of the present invention will be specifically described below.

(Synthesis Example 1-1 (Polymer Denaturer A1): Synthesis of 4- (Piperidin-1-yl) Phenyl) Metanon)
3.3 g (15.0 mmol) of 4,4'-difluorobenzophenone, 30 mL of dimethyl sulfoxide and 7.4 mL (75.0 mmol) of piperidine were placed in a glass reaction vessel, and the mixture was stirred at 80 ° C. for 22 hours. The reaction mixture is poured into ice water, the precipitate is collected by filtration, dried under vacuum, and then the solid purified by silica gel column chromatography (normal hexane: chloroform = 75: 25) is recrystallized from acetonitrile to form a bis as a pale yellow solid. (4- (Piperidine-1-yl) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (piperidine-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.58-1.71 (m, 12H), 3.33-3.35 (m, 8H), 6.87-6. 91 (m, 4H), 7.66-7.72 (m, 4H)
EI-MS; 348 (M)

(Synthesis Example 1-2 (Modifier B1 for Polymer): Synthesis of 4- (4-methylpiperazin-1-yl) phenyl) metanone)
3.3 g (15.0 mmol) of 4,4'-difluorobenzophenone, 30 mL of dimethyl sulfoxide, and 8.3 mL (75.0 mmol) of 1-methylpiperazine were placed in a glass reaction vessel, and the mixture was stirred at 100 ° C. for 24 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, vacuum dried, and the solid purified by silica gel column chromatography (normal hexane: chloroform = 65:35) was recrystallized from acetonitrile to form a bis (usual) as a yellow solid. 4- (4-Methylpiperazin-1-yl) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (4-methylpiperazin-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 2.30 (s, 6H), 2.51-2.54 (m, 8H), 3.32-3.35 (m, 8H), 6.88-6.92 (m, 4H), 7.67-7.71 (m, 4H)
EI-MS; 378 (M)

(Synthesis Example 1-3 (Modifier C1 for Polymer): Synthesis of 4- (3- (diethylamino) pyrrolidine-1-yl) phenyl) metanone)
2.6 g (12.0 mmol) of 4,4'-difluorobenzophenone, 48 mL of dimethyl sulfoxide, and 9.4 mL (60.0 mmol) of 3- (diethylamino) pyrrolidine were placed in a glass reaction vessel, and the mixture was stirred at 100 ° C. for 19 hours. .. The reaction mixture was poured into ice water, the precipitate was collected by filtration, dried under vacuum, and then the solid purified by silica gel column chromatography (normal hexane: chloroform = 60: 40) was recrystallized from normal hexane to form bis (normal hexane) as a yellow powder. 4- (3- (diethylamino) pyrrolidine-1-yl) phenyl) methanone was obtained.
The physical characteristics of the obtained bis (4- (4- (diethylamino) pyrrolidine-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.01-1.05 (t, 12H), 1.89-1.95 (m, 2H), 2.19-2. 21 (m, 2H), 2.61-2.71 (m, 8H), 3.14-3.19 (m, 2H), 3.33-3.40 (m, 4H), 3.48- 3.58 (m, 4H), 6.53-6.55 (m, 4H), 7.66-7.69 (m, 4H)
FD-MS; 462 (M)

(Synthesis Example 1-4 (Denaturant D1 for Polymer): Synthesis of 4- (4- (Pyrrolidine-1-yl) Piperidine-1-yl) Phenyl) Metanon)
In a glass reaction vessel, 2.2 g (10.0 mmol) of 4,4'-difluorobenzophenone, 40 mL of dimethyl sulfoxide, and 7.7 gr (50.0 mmol) of 4- (1-pyrrolidinyl) piperidine were placed at 100 ° C. for 17 hours. Stirred. The reaction mixture was poured into ice water, the precipitate was collected by filtration, and the vacuum-dried solid was recrystallized from chlorobenzene to form a pale yellow scale-like solid with bis (4- (4- (pyrrolidin-1-yl) piperidine-1). -Il) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (4- (pyrrolidin-1-yl) piperidine-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 1.61-1.68 (m, 4H), 1.70-1.86 (m, 8H), 1.99-2.02 ( m, 4H), 2.18-2.25 (m, 2H), 2.58-2.62 (m, 8H), 2.88-2.95 (m, 4H), 3.84-3. 89 (m, 4H), 6.88-6.92 (m, 4H), 7.70-7.74 (m, 4H)
FD-MS; 486 (M)

(Synthesis Example 1-5 (Modifier E1 for Polymer): Synthesis of 4- (4- (trifluoromethyl) piperidine-1-yl) phenyl) metanone)
In a glass reaction vessel, 2.2 g (10.0 mmol) of 4,4'-difluorobenzophenone, 40 mL of dimethyl sulfoxide, and 6.5 mL (50.0 mmol) of 4-trifluoromethylpiperidine were placed, and the mixture was stirred at 120 ° C. for 17 hours. .. The reaction mixture was poured into ice water, the precipitate was collected by filtration, and the vacuum-dried solid was recrystallized from acetonitrile to form a pale yellow scaly solid with bis (4- (4- (trifluoromethyl) piperidine-1-yl) phenyl. ) Obtained Methanon.
The physical characteristics of the obtained bis (4- (4- (trifluoromethyl) piperidine-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.57-1.76 (m, 4H), 1.96-2.00 (m, 4H), 2.23-2. 37 (m, 2H), 2.83-2.90 (m, 4H), 3.98 (d, 4H), 6.91-6.95 (m, 4H), 7.69-7.72 ( m, 4H)
EI-MS; 484 (M)

(Synthesis Example 1-6 (Polymer Denaturer F1): Synthesis of 4- (Pyrrolidine-1-yl) Phenyl) Metanon)
5.5 g (25.0 mmol) of 4,4'-difluorobenzophenone, 50 mL of dimethyl sulfoxide and 10.3 mL (125.0 mmol) of pyrrolidine were placed in a glass reaction vessel, and the mixture was stirred at 100 ° C. for 17 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, and the vacuum-dried solid was recrystallized from chloroform: hexane = 1: 2 to obtain bis (4- (pyrrolidin-1-yl) phenyl) methanone as a yellow solid. Obtained.
The physical characteristics of the obtained bis (4- (pyrrolidin-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 2.02-2.05 (m, 8H), 3.35-3.39 (m, 8H), 6.53-6.58 ( m, 4H), 7.74-7.77 (m, 4H)
EI-MS; 320 (M)

(Synthesis Example 1-7 (Polymer Denaturer G1): Synthesis of Bis (4-thiomorpholinophenyl) Metanone)
2.2 g (10.0 mmol) of 4,4'-difluorobenzophenone, 20 mL of dimethyl sulfoxide and 4.7 mL (50.0 mmol) of thiomorpholine were placed in a glass reaction vessel, and the mixture was stirred at 120 ° C. for 24 hours. Saturated sodium carbonate aqueous solution and chloroform are added to separate the organic layer, dried with magnesium sulfate, the solvent is distilled off under reduced pressure, and the solid purified by silica gel column chromatography (normal hexane: chloroform = 80: 20) is recrystallized from acetonitrile. Crystallization gave bis (4-thiomorpholinophenyl) methanone as a yellow needle-like solid.
The physical characteristics of the obtained bis (4-thiomorpholinophenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 2.70-2.73 (m, 8H), 3.76-3.78 (m, 8H), 6.86-6. 88 (m, 4H), 7.69-7.72 (m, 4H)
EI-MS; 384 (M)

(Synthesis Example 1-8 (Polymer Denaturer H1): Synthesis of Bis (4-morpholinophenyl) Metanone)
4.4 g (20.0 mmol) of 4,4'-difluorobenzophenone, 40 mL of dimethyl sulfoxide, and 8.7 mL (100.0 mmol) of morpholine were placed in a glass reaction vessel, and the mixture was stirred at 120 ° C. for 17 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, dried under vacuum, and then the solid purified by silica gel column chromatography (normal hexane: chloroform = 70:30) was recrystallized from acetonitrile to form a bis (yellow solid). 4-morpholinophenyl) metanone was obtained.
The physical characteristics of the obtained bis (4-morpholinophenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.27-3.30 (m, 8H), 3.82-3.85 (m, 8H), 6.89-6. 94 (m, 4H), 7.69-7.73 (m, 4H)
EI-MS; 352 (M)

(Synthesis Example 1-9 (Modifier I1 for Polymer): Synthesis of 4- (1,4-dioxa-8-azaspiro [4,5] decane-8-yl) phenyl) metanone)
2.2 g (10.0 mmol) of 4,4'-difluorobenzophenone, 40 mL of dimethyl sulfoxide, and 6.4 mL (50.0 mmol) of 4-piperidone ethylene ketal were placed in a glass reaction vessel, and the mixture was stirred at 100 ° C. for 16 hours. .. The reaction mixture is poured into ice water, the precipitate is collected by filtration, dried under vacuum, and the obtained solid is recrystallized from acetonitrile to form a yellow solid (4- (1,4-dioxa-8-azaspiro [4,4) dioxa-8-azaspiro]. 5] Decane-8-yl) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (1,4-dioxa-8-azaspiro [4,5] decane-8-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.78-1.85 (m, 8H), 3.48-3.55 (m, 8H), 3.97 (d, 8H), 6.90-6.93 (m, 4H)), 7.67-7.70 (m, 4H)
FD-MS; 464 (M)

(Synthesis Example 1-10 (Modifier for Polymer J1): Synthesis of phenyl (4- (4-pyrrolidin-1-yl) piperidine-1-yl) phenyl) metanone)
2.0 g (10.0 mmol) of 4-fluorobenzophenone, 40 mL of dimethyl sulfoxide, and 3.9 g (25.0 mmol) of 4- (1-pyrrolidinyl) piperidine were placed in a glass reaction vessel, and the mixture was stirred at 100 ° C. for 16 hours. The reaction mixture is poured into ice water, the precipitate is collected by filtration, dried under vacuum, and the obtained solid is recrystallized from diisopropyl ether to form a pale yellow solid, phenyl (4- (4-pyrrolidin-1-yl) piperidine-). 1-Il) phenyl) metanone was obtained.
The physical characteristics of the obtained phenyl (4- (4-pyrrolidin-1-yl) piperidine-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.73-1.74 (m, 2H), 1.75-1.76 (m, 4H), 1.95-1. 96 (m, 2H), 2.21-2.22 (m, 1H), 2.54-2.57 (m, 4H), 2.93-3.00 (m, 2H), 3.82- 3.86 (m, 2H), 6.89-6.91 (m, 2H), 7.52-7.54 (m, 3H), 7.68-7.74 (m, 4H)
EI-MS; 334 (M)

1-2. Production of Modified Conjugated Diene Polymer The following will specifically describe examples relating to the production of a modified conjugated diene polymer using the polymer modifier (1) of the present invention. The polymerization conditions, modification conditions and polymerization results are summarized in Table 1.

[Measurement method of physical properties, etc.]
(Catalytic activity)
The catalytic activity is the polymer yield (g) per 1 mmol of the central metal of the catalyst used in the polymerization reaction and 1 hour of the polymerization time. For example, when the catalyst is a gadolinium compound, the polymer yield (g) per 1 mmol of the gadolinium metal of the gadolinium compound used in the polymerization reaction and the polymerization time per hour.

(Ratio of cis, trans, vinyl of modified conjugated diene polymer (mol%))
Using infrared absorption spectrum analysis, the ratio of cis, trans, and vinyl (mol%) was calculated from the absorption intensity ratios of ^{cis 734 cm -1} (cis), 967 cm ^-1 (trans), and 912 cm ^{-1 (vinyl).}

(Number average molecular weight (Mn) and weight average molecular weight (Mw))
Performed by the GPC (manufactured by Shimadzu Corporation) method at a temperature of 40 ° C. using polystyrene as a standard substance and tetrahydrofuran as a solvent, and calculated using a calibration curve obtained from the obtained molecular weight distribution curve, and has a number average molecular weight and a weight average molecular weight. Asked.

(Molecular weight distribution)
It was evaluated by Mw / Mn, which is a ratio of weight average molecular weight Mw and number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.

(Moony viscosity (ML _{1 + 4} , 100 ° C))
_{The Mooney viscosity of rubber (ML 1 + 4} , 100 ° C.) was determined by preheating at 100 ° C. for 1 minute using a Mooney viscometer manufactured by Shimadzu Corporation in accordance with JIS-K6300-1 and then measuring for 4 minutes.

(Tensile stress (50%, 100%, 300%))
50%, 100%, and 300% tensile stresses were measured according to JIS-K6251. Comparative example C-1 in Table 3 was expressed as 100 as an exponential notation. The larger the index, the better the characteristics (breaking stress).

(Breaking strength)
The stress at break was measured according to JIS-K6251. Comparative example C-1 in Table 17 was expressed as 100 as an exponential notation. The larger the index, the better the characteristics (breaking strength).

(Repulsive elasticity)
The rebound resilience was measured at room temperature using a Dunlop tripsometer according to JIS-K6255. Comparative example C-1 in Table 3 was expressed as 100 as an exponential notation. The larger the index, the better the characteristics (rebound resilience).

(Pico wear)
The measurement was performed according to the measurement method specified in JIS K6264-2. Comparative example C-1 in Table 3 was expressed as 100 as an exponential notation. The larger the index, the better the characteristics (pico wear).

(Fuel efficiency (tan δ (3%)))
Using a viscoelasticity measuring device (RPA2000 manufactured by Alpha Technologies), the measurement was performed at a temperature of 150 ° C., a frequency of 1 Hz, and a dynamic strain of 3%. Comparative example is shown as an index with 100 as 100. The smaller the value of fuel efficiency (tan δ), the better the characteristics, but in Table 3, the larger the index, the better the characteristics (low loss).

(Fuel efficiency (tan δ (60 ° C)))
Using a viscoelasticity measuring device (VR-7130, manufactured by Ueshima Seisakusho Co., Ltd.), the measurement was performed in a temperature range of -60 ° C to 80 ° C, a frequency of 16 Hz, and a dynamic strain of 0.5%. Tan δ at 60 ° C. was used as an index of fuel efficiency. Comparative Example C-1 shown in Table 3 was expressed as 100 in an exponential notation. The smaller the value of fuel efficiency (tan δ), the better the characteristics, but in Table 3, the larger the index, the better the characteristics (fuel efficiency).

(Dispersibility of filler)
The dispersibility of the filler in the modified conjugated diene polymer composition was evaluated by the strain dependence (Pain effect) of the storage elastic modulus (G'). Dynamic strain analysis was performed under the conditions of a frequency of 150 ° C. and 1 Hz using a rubber workability analyzer RPA-2000 manufactured by Alfar Technology Co., Ltd. The Pain effect was evaluated by the ratio of G'at 25% strain to G'at 0.5% strain (G'0.5% / G'25%). Comparative Example C-1 shown in Table 3 was expressed as 100 in an exponential notation. The larger the index, the better the dispersibility of the filler.

(Low temperature characteristic (-30 ° C storage elastic modulus (E')): Using a viscoelasticity measuring device (VR-7130, manufactured by Ueshima Seisakusho Co., Ltd.), the temperature range is -60 to 80 ° C., the frequency is 16 Hz, and the dynamic strain is 0. It was measured under the condition of 5%, and the storage elastic modulus (E') at -30 ° C was used. Comparative Example C-1 shown in Table 3 was indexed as 100 (the larger the index, the more elastic at -30 ° C). Low rate and good).

(Example A1-1)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 490 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then 3.5 mL of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 4.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 10.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 6.7 mL of a toluene solution (0.06 mol / L) of the polymer modifier A1 was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours.

(Example A1-2)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer denaturant A1 was changed to 8 ml of the polymer denaturant B1 (0.05 mol / L) and the amount of triethylaluminum (TEAL) was 3.0 ml. rice field.

(Example A1-3)
The experiment was carried out in the same manner as in Example A1-1 except that the polymer modifier A1 was changed to 8 ml of the polymer modifier C1 (0.05 mol / L).

(Example A1-4)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer modifier A1 was changed to polymer modifier D1 (0.05 mol / L) 8 ml and triethylaluminum (TEAL) was changed to 3.0 ml. rice field.

(Example A1-5)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer denaturant A1 was changed to 8 ml of the polymer denaturant E1 (0.05 mol / L) and the amount of triethylaluminum (TEAL) was 3.6 ml. rice field.

(Example A1-6)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer modifier A1 was changed to polymer modifier F1 (0.05 mol / L) 8 ml and triethylaluminum (TEAL) was changed to 2.8 ml. rice field.

(Example A1-7)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer modifier A1 was changed to polymer modifier G1 (0.05 mol / L) 8 ml and triethylaluminum (TEAL) was changed to 3.1 ml. rice field.

(Example A1-8)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer denaturant A1 was changed to 8 ml of the polymer denaturant H1 (0.05 mol / L) and the amount of triethylaluminum (TEAL) was 3.2 ml. rice field.

(Example A1-9)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer denaturant A1 was changed to 8 ml of the polymer denaturant I1 (0.05 mol / L) and the amount of triethylaluminum (TEAL) was 3.0 ml. rice field.

(Example A1-10)
Experiments were carried out in the same manner as in Example A1-1 except that the polymer modifier A1 was changed to polymer modifier J1 (0.05 mol / L) 8 ml and triethylaluminum (TEAL) was changed to 3.0 ml. rice field.

(Comparative Example A1-1)
The experiment was carried out in the same manner as in Example A1-1 except that the polymerization was stopped without adding a denaturing agent.

(Example B1-1)
The flask was replaced with nitrogen, _{and 0.155 mL of a toluene solution (0.425 mol / L) of neodymium trisversatic acid (Nd (Ver) 3} ) and 0.20 mL of a cyclohexane solution (2 mol / L) of diethylaluminum chloride and diisobutylaluminum hydride. A ripening catalyst solution was prepared by reacting 0.33 mL of a cyclohexane solution (2 mol / L).
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 250 mL of cyclohexane solvent and 250 mL of butadiene was charged. Then 1.0 mL of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 0.16 mL of the aging catalyst solution was added, polymerized at 40 ° C. for 10 minutes, and then 5.0 mL of the orthodichlorobenzene solution (0.05 mol / L) of the polymer modifier D1 was added at the same temperature. A denaturation reaction was carried out for 10 minutes. 3 mL of an ethanol solution containing an anti-aging agent was added to terminate the polymerization reaction. Then, after releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 100 ° C. for 2 hours.

(Example B1-2)
The flask was replaced with nitrogen, 1.63 mL of a toluene solution (0.04 mol / L) of tris (2-ethylhexyl phosphate) neodymium (Nd (DEHP) ₃ ) and 0.20 mL of a cyclohexane solution of diethylaluminum chloride (2 mol / L). And 0.33 mL of a cyclohexane solution (2 mol / L) of diisobutylaluminum hydride was reacted to prepare an aging catalyst solution.
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 250 mL of cyclohexane solvent and 250 mL of butadiene was charged. Then 1.0 mL of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 1.0 mL of the aging catalyst solution was added, polymerized at 40 ° C. for 10 minutes, and then 5.0 mL of the orthodichlorobenzene solution (0.05 mol / L) of the polymer modifier D1 was added at the same temperature. A denaturation reaction was carried out for 10 minutes. 3 mL of an ethanol solution containing an anti-aging agent was added to terminate the polymerization reaction. Then, after releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 100 ° C. for 2 hours.

(Example B1-3)
The flask was replaced with nitrogen, _{and 9.8 mL of a toluene solution of Nd (DEHP) 3} (0.04 mol / L), 13.8 mL of a cyclohexane solution of butadiene (10 wt%) and a cyclohexane solution of diisobutylaluminum hydride (2 mol / L) 0. After reacting 78 mL, 0.60 mL of a cyclohexane solution (2 mol / L) of diethylaluminum chloride was added and further reacted to prepare a aging catalyst solution.
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 550 mL of cyclohexane solvent and 75 mL of butadiene was charged. Then, 0.50 mL of a cyclohexane solution (2 mol / L) of triisobutylaluminum (TIBA) was added. Next, 8.0 mL of the aging catalyst solution was added, polymerized at 50 ° C. for 15 minutes, and then 10.0 mL of an orthodichlorobenzene solution (0.05 mol / L) of the polymer modifier D1 was added at the same temperature. A denaturation reaction was carried out for 10 minutes. 3 mL of an ethanol solution containing an anti-aging agent was added to terminate the polymerization reaction. Then, after releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 100 ° C. for 2 hours.

(Comparative Example B1-1)
The experiment was carried out in the same manner as in Example B1-1 except that the aging catalyst solution was 0.315 mL, 3 mL of an ethanol solution containing an antioxidant was added without adding a denaturing agent, and the polymerization reaction was stopped.

(Comparative Example B1-2)
The experiment was carried out in the same manner as in Example B1-2 except that 3 mL of an ethanol solution containing an antioxidant was added without adding a denaturing agent to stop the polymerization reaction.

(Comparative Example B1-3)
Experiments were carried out in the same manner as in Example B1-3 except that the amount of triisobutylaluminum (TIBA) was 0.625 mL, 3 mL of an ethanol solution containing an antioxidant was added without adding a denaturing agent, and the polymerization reaction was stopped. rice field.

The polymerization results of Examples A1-1 to A1-10 and Comparative Example A1-1 are shown in Table 1, and the polymerization results of Examples B1-1 to B1-3 and Comparative Examples B1-1 to B1-3 are shown in Table 2. Indicated.

Since the modified polybutadienes of Examples A1-1 to A1-10 have a larger UV / RI value obtained by GPC analysis than the unmodified polybutadienes of Comparative Example A1-1, various modifiers are bound to the polybutadienes ( It is suggested that it is denatured).
Further, since the modified polybutadienes of Examples B1-1 to B1-3 have a larger UV / RI value obtained by GPC analysis than the unmodified polybutadienes of Comparative Examples B1-1 to B1-3, various modifiers are polybutadienes. It is suggested that it is bound (denatured) to.

1-3. Production of Modified Conjugated Diene Polymer Composition (Rubber Composition) (Example C1-1)
Using the modified polybutadiene of Example A1-1, natural rubber (50 parts by mass), carbon black (dia black manufactured by Mitsubishi Chemical Co., Ltd.) (50 parts by mass), zinc oxide (50 parts by mass) were added to the modified polybutadiene (50 parts by mass) with a plastomill. 3 parts by mass), stearic acid (2 parts by mass), anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) (2 parts by mass), oil (Viva Tech 400 manufactured by H & R) (3 parts by mass) and knead. Perform the primary compounding, and then perform the secondary compounding by adding the vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) (1 part by mass) and sulfur (1.5 parts by mass) by roll. To prepare a compounded rubber (rubber composition). Further, this compounded rubber was molded according to the target physical characteristics, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured.

(Example C1-2)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-2 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-3)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-3 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-4)
A compounded rubber was prepared in the same manner as in Example C-1 except that the modified polybutadiene of Example A1-4 was used instead of the modified polybutadiene of Example A-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-5)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-5 was used instead of the modified polybutadiene of Example A-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-6)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-6 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-7)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-7 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-8)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-8 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-9)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-9 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C1-10)
A compounded rubber was prepared in the same manner as in Example C1-1 except that the modified polybutadiene of Example A1-10 was used instead of the modified polybutadiene of Example A1-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Comparative Example C-1)
The compounded rubber was prepared in the same manner as in Example C1-1 except that JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene of Example A1-1. The physical properties of the vulcanized product prepared, molded, and press-vulcanized were measured.
Table 3 shows the measurement results of the physical properties of the modified conjugated diene polymer composition (rubber composition) of each Example and Comparative Example.

The numerical values in Table 3 are based on each characteristic value of Comparative Example C-1 using unmodified polybutadiene (JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation) as a reference (100). When this is done, each item is displayed in exponential notation. The larger the value, the better the characteristics.

As shown in Table 3, the conjugated diene polymer compositions (rubber compositions) of Examples C1-1 to C1-10 using the modified conjugated diene polymers of Examples A1-1 to A1-10 are unmodified. Compared to the conjugated diene polymer composition (rubber composition) of Comparative Example C-1 using a conjugated diene polymer, fuel efficiency (tan δ), low temperature characteristics, filler dispersibility, impact resilience, abrasion resistance, and tensile stress Is excellent.

2-1. Polymer modifiers (1) "(A ¹ and A ^{2 in} formula (1) are 6-membered ring aromatic heterocyclic groups containing at least one nitrogen atom as a ring constituent element, and R ¹ and R ² are. , Saturated 3- to 12-membered ring heterocyclic group) ”Synthesis example The synthesis example of the polymer modifier of the present invention will be specifically described below.

(Synthesis Example 2-1 (Synthesis of Raw Material for Bis (6-bromopyridin-3-yl) Metanone): Synthesis of Bis (6-Bromopyridine-3-yl) Methanol)
Put 250 mL of tetrahydrofuran in a glass reaction vessel, cool to -75 ° C, 11.3 mL of n-butyllithium (17.5 mmol: concentration 1.55 M / n-hexane solution), 8.8 mL of n-butylmagnesium chloride (8). .75 mmol: concentration 1.0 M / tetrahydrofuran solution) was added to bring it to −10 ° C., then cooled to −75 ° C. again, and 2-bromo-5-iodopyridine was added to bring it to −15 ° C. The mixture was cooled to −75 ° C. again, 6-bromo-3-pyridinecarboxyaldehyde was added, and the reaction was carried out overnight at room temperature.
Saturated ammonium chloride chloride and chloroform are added to separate the organic layer, dried with magnesium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography (chloroform: ethyl acetate = 9: 1) to form bis (6-) as a white solid. Bromopyridine-3-yl) methanol was obtained.
The physical characteristics of the obtained bis (6-bromopyridin-3-yl) methanol were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.21 (d, 1H), 5.88 (d, 1H), 7.33-7.60 (m, 4H), 8 .35 (s, 2H)
EI-MS; 344 (M)

(Synthesis Example 2-2 (Synthesis of raw materials for polymer modifiers A2, B2 and C2): Synthesis of bis (6-bromopyridin-3-yl) metanone)
In a glass reaction vessel, 15.6 g (45.2 mmol) acetonitrile of bis (6-bromopyridin-3-yl) methanol 150 mL, 18.1 g (29.4 mmol) of potassium peroxymonosulfate, 2-iodo-5-methylbenzene. 152.1 mg (0.45 mmol) of potassium sulfonate was added and reacted at 70 ° C. Chloroform was added, the insoluble material was filtered off, and the solvent was distilled off under reduced pressure. The obtained yellow solid was purified by silica gel column chromatography (chloroform), and the compound bis (6-bromopyridine-3-yl) was obtained as a white solid. Obtained Metanon.
The physical characteristics of the obtained bis (6-bromopyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 7.68-7.71 (m, 2H), 7.96-7.98 (m, 2H), 8.71-8. 72 (m, 2H)
EI-MS; 341 (M)

(Synthesis Example 2-3 (Denaturant A2 for Polymer): Synthesis of Bis (6- (Pyrrolidine-1-yl) Pyridine-3-yl) Metanone)
Put 2.4 g (7.0 mmol) of bis (6-bromopyridin-3-yl) methanone and 14 mL of tetrahydrofuran in a glass reaction vessel having a capacity of 100 mL equipped with a stirrer, cool to −75 ° C., and then pyrrolidine 2. 9 mL (35.0 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, and the solid obtained after vacuum drying was recrystallized from toluene to obtain the compound bis (6- (pyrrolidin-1-yl) pyridine-3-yl) as a pale yellow solid. ) Obtained Metanon.
The physical characteristics of the obtained bis (6- (pyrrolidin-1-yl) pyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 2.01-2.34 (m, 8H), 3.52 (br, 8H), 6.39-6.41 (m, 2H), 7.87-7.90 (m, 2H), 8.53-8.54 (m, 2H)
EI-MS; 322 (M)

(Synthesis Example 2-4 (Denaturant B2 for Polymer): Synthesis of Bis (6- (3-diethylamino) Pyrrolidine-1-yl) Pyridine-3-yl) Metanone)
In a glass reaction vessel, 3.8 g (11.0 mmol) of bis (6-bromopyridin-3-yl) methanone and 44 mL of tetrahydrofuran were placed and cooled to 0 ° C., and then 3- (diethylamino) pyrrolidine (8.7 mL) (55. 0 mmol) was added, and the mixture was stirred at room temperature for 21 hours. Tetrahydrofuran was distilled off under reduced pressure, and then a solid purified by silica gel column chromatography (chloroform: normal hexane = 3: 2) was recrystallized from diisopropyl ether to obtain bis ((6- (3-diethylamino) pyrrolidine-) as a pale yellow solid. 1-Il) pyridine-3-yl) metanone was obtained.
The physical characteristics of the obtained bis (6- (3-diethylamino) pyrrolidine-1-yl) pyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.01-1.04 (t, 12H), 1.88-1.94 (m, 2H), 2.20-2. 24 (m, 2H), 2.62-2.71 (m, 8H), 3.21-3.82 (m, 6H), 5.32 (br, 3H), 6.38-6.41 ( m, 2H), 7.88-7.91 (m, 2H), 8.53-8.54 (m, 2H)
FD-MS; 464 (M)

(Synthesis Example 2-5 (Modifier C2 for Polymer): Synthesis of bis (6- (4- (pyrrolidin-1-yl) piperidine-1-yl) pyridin-3yl) metanone)
Put 3.8 g (11.0 mmol) of bis (6-bromopyridin-3-yl) methanone and 110 mL of N, N-dimethylformamide in a glass reaction vessel, cool to 0 ° C., and then 4- (1-pyrrolidinyl). 8.5 g (55.0 mmol) of piperidine was added, and the mixture was stirred at 50 ° C. for 17 hours. The reaction mixture is poured into ice water, the precipitate is collected by filtration, dried under vacuum, and the obtained solid is recrystallized from chlorobenzene to form a pale yellow solid with bis (6- (4- (pyrrolidin-1-yl) piperidine-). 1-Il) Pyridine-3yl) Metanone was obtained.
The physical characteristics of the obtained bis (6- (4- (pyrrolidin-1-yl) piperidine-1-yl) pyridine-3yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CDCl ₃ ; δ (ppm)); 1.53-1.63 (m, 4H), 1.77-1.84 (m, 8H), 1.99-2.03 ( m, 4H), 2.28-2.34 (m, 2H), 2.62 (br, 8H), 3.01-3.08 (m, 4H), 4.40-4.43 (m, 4H), 6.66-6.68 (m, 2H), 7.93-7.95 (m, 2H), 8.595-8.60 (m, 2H)
FD-MS; 488 (M)

2-2. Production of Modified Conjugated Diene Polymer The following will specifically describe examples relating to the production of a modified conjugated diene polymer using the polymer modifier (1) of the present invention. The polymerization conditions, modification conditions and polymerization results are summarized in Table 4.

[Measurement method of physical properties, etc.]
Since the content is the same as that described in the column of [Measurement method of physical property value] in "1-2. Production of modified conjugated diene polymer", the description thereof will be omitted.

(Example A2-1)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 490 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then 3.5 mL of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 4.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 10.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 8.0 mL of a toluene solution (0.05 mol / L) of the polymer modifier A2 was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. Other polymerization results are shown in Table 4.

(Example A2-2)
Experiments were carried out in the same manner as in Example A2-1 except that the polymer modifier A2 was changed to polymer modifier B2 (0.05 mol / L) 8 ml and triethylaluminum (TEAL) was changed to 3.2 ml. rice field.

(Example A2-3)
Experiments were carried out in the same manner as in Example A2-1 except that the polymer modifier A2 was changed to polymer modifier C2 (0.05 mol / L) 8 ml and triethylaluminum (TEAL) was changed to 3.1 ml. rice field.

(Comparative Example A2-1)
The experiment was carried out in the same manner as in Example A2-1 except that the polymerization was stopped without adding a denaturing agent. The polymerization results are shown in Table 4.

Since the modified polybutadiene of Examples A2-1 to A2-3 has a larger UV / RI value obtained by GPC analysis than the unmodified polybutadiene of Comparative Example A2-1, the modifying agent is bound to the polybutadiene. It is suggested that it is (denatured).

2-3. Production of Modified Conjugated Diene Polymer Composition (Rubber Composition) (Example C2-1)
Using the modified polybutadiene of Example A2-1, vulcanized polybutadiene (50 parts by mass) with a plast mill, natural rubber (50 parts by mass), carbon black (Diablack manufactured by Mitsubishi Chemical Corporation) (50 parts by mass), zinc oxide (50 parts by mass). 3 parts by mass), stearic acid (2 parts by mass), anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) (2 parts by mass), oil (Viva Tech 400 manufactured by H & R) (3 parts by mass) and knead. Perform the primary compounding, and then perform the secondary compounding by adding the vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) (1 part by mass) and sulfur (1.5 parts by mass) by roll. To prepare a compounded rubber (rubber composition). Further, this compounded rubber was molded according to the target physical characteristics, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured.

(Example C2-2)
A compounded rubber was prepared in the same manner as in Example C2-1 except that the modified polybutadiene of Example A2-2 was used instead of the modified polybutadiene of Example A2-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Example C2-3)
A compounded rubber was prepared in the same manner as in Example C2-1 except that the modified polybutadiene of Example A2-3 was used instead of the modified polybutadiene of Example A2-1, and the vulcanized product was molded and press vulcanized. Physical properties were measured.

(Comparative Example C-1)
Formulated in the same manner as in Example C2-1 except that JSR BR01 (unmodified polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene of Example A2-1. Rubber was prepared, molded, and press-vulcanized to measure the physical properties of the vulcanized product.
Table 5 shows the measurement results of the physical properties of the modified conjugated diene polymer composition (rubber composition) of each Example and Comparative Example.

The numerical values in Table 5 are based on each characteristic value of Comparative Example C2-1 using unmodified polybutadiene (JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation) as a reference (100). When this is done, each item is displayed in exponential notation. The larger the value, the better the characteristics.

As shown in Table 5, the modified conjugated diene polymer composition (rubber composition) of Example C2-1 using the modified conjugated diene polymer of Examples C2-1 to C2-3 has an unmodified conjugated diene weight. It is superior in fuel efficiency (tan δ), low temperature characteristics, filler dispersibility, rebound resilience, abrasion resistance, and tensile stress to the conjugated diene polymer composition (rubber composition) of Comparative Example C-1 using the coalescence. There is.

3-1. Polymer modifiers (2) Synthesis examples of "Classification (1)" Hereinafter, synthetic examples of polymer modifiers will be specifically described.

Synthesis Example 3-1: Synthesis of (4- (diethylamino) phenyl) (4- (trifluoromethyl) phenyl) methanone (polymer modifier A3) In a glass reaction vessel, 1-bromo-4-trifluoromethyl 276 μL (2.0 mmol) of benzene and 10 mL of tetrahydrofuran were added, 1.35 mL (2.1 mmol) of an n-hexane solution of n-butyllithium (1.55 mol / L) was added, and the mixture was stirred. Then, 4-diethylaminobenzonitrile was added, and the mixture was further stirred. Tetrahydrofuran was distilled off under reduced pressure, n-hexane and a 2N hydrochloric acid aqueous solution were added, and the mixture was stirred. After separating the organic layer, the mixture was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to prepare a yellow solid compound (4- (diethylamino) phenyl) (4). -(Trifluoromethyl) phenyl) methanone was obtained.
The physical characteristics of the obtained (4- (diethylamino) phenyl) (4- (trifluoromethyl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 1.17-1.22 (t, 6H), 3.42-3.47 (q, 4H), 6.66-6. 68 (m, 2H), 7.70-7.79 (m, 6H)
EI-MS; 321 (M)

Synthesis Example 3-2: Synthesis of (4- (1-methyl-1H-imidazol-2-yl) phenyl) (4- (trifluoromethyl) phenyl) methanone (polymer modifier B3) (1) 4- Synthesis of (1-methylimidazol-2-yl) benzonitrile To a glass reaction vessel, 2.4 mL (30.0 mmol) of 1-methylimidazole and 250 mL of tetrahydrofuran were added, followed by an n-hexane solution of n-butyllithium (n-hexane solution). 20.3 mL (31.5 mmol) of 1.55 mol / L) was added, and the mixture was stirred. Then, 30 mL (30 mmol) of a solution of zinc (II) chloride in tetrahydrofuran (1.0 mol / L) was added, and the mixture was stirred. To the obtained suspension, 4.55 g (25 mmol) of 4-bromobenzonitrile and 2.89 g (2.5 mmol) of tetrakistriphenylphosphine palladium were added, and the mixture was reacted at 55 ° C. for 16 hours. After quenching by adding methanol, the solvent was distilled off, a 2N aqueous hydrochloric acid solution was added to the organic layer extracted with chloroform, the aqueous solution layer was separated, an aqueous sodium hydroxide solution was added to make the system alkaline, and then the mixture was extracted with chloroform. , Drying with magnesium sulfate and distilling off the solvent under reduced pressure to give compound 4- (1-methylimidazol-2-yl) benzonitrile as a white solid.
The physical characteristics of the obtained 4- (1-methylimidazol-2-yl) benzonitrile were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.78 (s, 3H), 7.04 (d, 1H), 7.11 (d, 1H), 7.73-7 .82 (m, 4H)
EI-MS; 183 (M)
(2) Synthesis of (4- (1-methylimidazol-2-yl) phenyl) (4- (trifluoromethyl) phenyl) methanone In a glass reaction vessel, 190 mL of tetrahydrofuran was placed and n-hexane of n-butyllithium was added. After adding 8.7 mL (13.4 mmol) of the solution (1.55 mol / L) and 6.71 mL (6.71 mmol) of the tetrahydrofuran solution (1 mol / L) of n-butylmagnesium chloride, 1-bromo-4-tri. 2.6 mL (19.2 mmol) of fluoromethylbenzene was added. Next, 3.5 g (19.2 mmol) of 4- (1-methylimidazol-2-yl) benzonitrile synthesized in (1) above was added, and the mixture was stirred at room temperature. Tetrahydrofuran was distilled off under reduced pressure, chloroform and a 2N hydrochloric acid aqueous solution were added, and the mixture was stirred for 1 hour. After the organic layer is separated, it is dried over magnesium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography (chloroform: ethyl acetate = 6: 4) to form a white solid compound (4- (1-methylimidazole-2). -Il) phenyl) (4- (trifluoromethyl) phenyl) metanone was obtained.
The physical characteristics of the obtained (4- (1-methylimidazol-2-yl) phenyl) (4- (trifluoromethyl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.82 (s, 3H), 7.06 (d, 1H), 7.12 (d, 1H), 7.78-7 .94 (m, 8H)
EI-MS; 330 (M)

3-2. Production of Modified Conjugated Diene Polymer The following specifically describes a reference example relating to the production of a modified conjugated diene polymer using the above-mentioned modifier for polymer (2). The polymerization conditions, modification conditions and polymerization results are summarized in Table 8.

[Measurement method of physical properties, etc.]
Since the content is the same as that described in the column of [Measurement method of physical property value] in "1-2. Production of modified conjugated diene polymer", the description thereof will be omitted.

(Reference Example A-1A)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 480 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then, 3.2 mL of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 4.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 10.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 10.0 mL of a toluene solution (0.05 mol / L) of the polymer modifier A3 was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. Other polymerization results are shown in Table 6.

(Reference Example A-2A)
The experiment was carried out in the same manner as in Reference Example A-1A except that the polymer modifier A3 was changed to the polymer modifier B3. The polymerization results are shown in Table 6.

(Comparative Example A-1)
Experiments were carried out in the same manner as in Reference Example A-1A, except that triethylaluminum (TEAL) was adjusted to 3.0 mL, 5 mL of an ethanol solution containing an antiaging agent was added without adding a denaturing agent, and the polymerization reaction was stopped. rice field. The polymerization results are shown in Table 6.

Since the modified polybutadienes of Reference Examples A-1A and A-2A have a larger UV / RI value obtained by GPC analysis than the unmodified polybutadienes of Comparative Example A-1, various modifiers are bound to the polybutadienes. It is suggested that it is (denatured).

(Reference Example B-1A)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 450 ml of cyclohexane solvent and 50 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.28 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerizing at 80 ° C. for 15 minutes, 7.5 mL of a toluene solution (0.05 mol / L) of the polymer modifier A was added, and a denaturation reaction was carried out at 20 ° C. for 10 minutes. Next, 3 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The yield was 60.2 g / L. Other polymerization results are shown in Table 7.

(Reference Example B-2A)
Modified polybutadiene was synthesized in the same manner as in Reference Example B-1A, except that the polymer modifier A was changed to the polymer modifier B. The yield was 59.2 g / L. Other polymerization results are shown in Table 7.

(Comparative Example B-1)
Cyclohexane was 540 ml, butadiene was 60 ml, n-butyllithium was 0.20 ml, and 5 ml of an ethanol solution containing an antiaging agent was added without adding a denaturing agent, in the same manner as in Reference Example B-1A. Modified polybutadiene was synthesized. The yield was 68.0 g / L. Other polymerization results are shown in Table 7.

Since the modified polybutadienes of Reference Examples B-1A and B-2A have higher UV / RI values obtained by GPC analysis than the unmodified polybutadienes of Comparative Example B-1, the modifier is bound to the polybutadienes ( It is suggested that it is denatured).

3-3. Production of Modified Conjugated Diene Polymer Composition (Rubber Composition) (Reference Example C-1A)
Reference Example Using the modified polybutadiene of A-1A, modified polybutadiene (50 parts by mass), natural rubber (50 parts by mass), carbon black (Diablack manufactured by Mitsubishi Chemical Corporation) (50 parts by mass), zinc oxide by vulcanization. Add (3 parts by mass), stearic acid (2 parts by mass), anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) (2 parts by mass), and oil (Viva Tech 400 manufactured by H & R) (3 parts by mass) and knead. The primary formulation is carried out, and then the secondary formulation is carried out by adding a vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) (1 part by mass) and sulfur (1.5 parts by mass) on a roll. As a result, a compounded rubber (rubber composition) was produced. Further, this compounded rubber was molded according to the target physical characteristics, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured. Table 8 shows the results of measuring the physical characteristics of various formulations.

(Reference Example C-2A)
A compounded rubber was prepared in the same manner as in Reference Example C-1A except that the modified polybutadiene of Reference Example A-2A was used instead of the modified polybutadiene of Reference Example A-1A, and was molded and press-vulcanized. The physical properties of the vulcanized product were measured. Table 8 shows the results of measuring the physical characteristics of various formulations.

(Comparative Example C-1)
Formulated in the same manner as in Reference Example C-1A except that JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene of Reference Example A-1A. Rubber was prepared, molded, and press-vulcanized to measure the physical properties of the vulcanized product. Table 8 shows the results of measuring the physical characteristics of various formulations.

The numerical values in Table 8 are each item when each characteristic value of Comparative Example C-1 using JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation is used as a reference (100). Each is displayed in exponential notation. The larger the value, the better the characteristics.

As shown in Table 8, the rubber compositions of Reference Examples C-1A and C-2A using the modified polybutadienes obtained from Reference Examples A-1A and A-2A were polymerized using JSR BR01 (Ni-based catalyst). It is superior in tensile stress, rebound resilience, abrasion resistance, and fuel efficiency (tan δ) to the rubber composition of Comparative Example C-1 using the above-mentioned polybutadiene).

4-1. Polymer modifiers (1) "A ¹ and A ^{2 in} formula (1) are 6-membered ring aromatic ring groups, and R ¹ and R ² are unsaturated 3- to 12-membered ring heterocyclic groups. Synthesis Examples of "Compounds" Specific examples of synthesis of polymer modifiers will be described below.

Synthesis Example 4-1: Synthesis of bis (4- (1-methyl-1H-imidazol-2-yl) phenyl) metanone (modifier A4 for polymer) In a glass reaction vessel, 2.4 mL of 1-methylimidazole ( Add 100 mL of 30.0 mmol) tetrahydrofuran, cool to −75 ° C., add 20.3 mL of normal butyllithium (31.5 mmol: concentration 1.55 M / n-hexane solution), stir, and then 30.0 mL of zinc chloride (30.0 mmol). 30.0 mmol: concentration 1.0 M / tetrahydrofuran solution) was added, and the mixture was stirred at room temperature for 1 hour. 3.4 g (10.0 mmol) of 4,4'-dibromobenzophenone and 1.16 g (1.0 mmol) of tetrakistriphenylphosphine palladium were added, and the mixture was reacted at 55 ° C. for 18 hours. After adding methanol and quenching, the solvent was distilled off and the mixture was extracted with chloroform. The solid was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: normal hexane = 6: 4) was recrystallized from toluene to obtain a compound bis (4- (1- (1- (1-) 1-)) as a white solid. Methyl-1H-imidazol-2-yl) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (1-methyl-1H-imidazol-2-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.82 (s, 6H), 7.05 (d, 2H), 7.12 (d, 2H), 7.80-7 .83 (m, 4H), 7.90-7.93 (m, 4H)
EI-MS; 342 (M)

Synthesis Example 4-2: Synthesis of bis (4- (1-phenyl-1H-imidazol-2-yl) phenyl) metanone (polymer modifier B4) In a glass reaction vessel, 1-phenylimidazole 5.7 mL ( 45.0 mmol) Tetrahydrofuran 150 mL is added, cooled to −75 ° C., normal butyllithium 30.5 mL (47.3 mmol: concentration 1.55 M / normal hexane solution) is added, and after stirring, zinc chloride 45.0 mL (45). After adding (0.0 mmol: concentration 1.0 M / tetrahydrofuran solution), the mixture was stirred at room temperature for 1 hour. 5.1 g (15.0 mmol) of 4,4'-dibromobenzophenone and 1.73 g (1.5 mmol) of tetrakistriphenylphosphine palladium were added, and the mixture was reacted at 55 ° C. for 17 hours. After adding methanol and quenching, the solvent was distilled off and the mixture was extracted with chloroform. The solid was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: normal hexane = 7: 3) was recrystallized from toluene to obtain a compound bis (4- (1- (1- (1-) 1-)) as a white solid. Phenyl-1H-imidazol-2-yl) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (1-phenyl-1H-imidazol-2-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 7.23-7.26 (m, 8H), 7.43-7.50 (m, 10H), 7.63-7. 65 (m, 4H)
EI-MS; 466 (M)

Synthesis Example 4-3: Synthesis of bis (4- (1-methyl-1H-pyrazol-5-yl) phenyl) metanone (modifier C4 for polymer) In a glass reaction vessel, 3.7 mL (45.0 mmol) of pyrazole ) Tetrahydrofuran 150 mL is added, cooled to −75 ° C., normal butyllithium 30.1 mL (47.3 mmol: concentration 1.57 M / n-hexane solution) is added, and after stirring, zinc chloride 45.0 mL (45.0 mmol) is added. : Concentration 1.0 M / tetrahydrofuran solution) was added, and the mixture was stirred at room temperature for 1 hour. 5.1 g (15.0 mmol) of 4,4'-dibromobenzophenone and 1.73 g (1.5 mmol) of tetrakistriphenylphosphine palladium were added, and the mixture was reacted at 55 ° C. for 17 hours. After adding methanol and quenching, the solvent was distilled off and the mixture was extracted with chloroform. The solid was dried with magnesium sulfate, the solvent was distilled off under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: ethyl acetate = 95: 5) was recrystallized from acetonitrile to obtain compound bis (4- (1- (1- (1-) 1-)) as a yellow solid. Methyl-1H-pyrazole-5-yl) phenyl) metanone was obtained.
The physical characteristics of the obtained bis (4- (1-methyl-1H-pyrazole-5-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.94 (s, 6H), 6.42 (d, 2H), 7.51 (d, 2H), 7.59-7 .62 (m, 4H), 7.90-7.93 (m, 4H)
EI-MS; 342 (M)

Synthesis Example 4-4: Synthesis of bis (4- (1H-pyrrole-1-yl) phenyl) metanone (polymer modifier D4) 4.4 g (20) of 4,4'-difluorobenzophenone in a glass reaction vessel. .0 mmol), 19.6 g (60.0 mmol) of cesium carbonate, 80 mL of dimethyl sulfoxide and 3.5 mL (50.0 mmol) of pyrrole were added, and the mixture was stirred at 80 ° C. for 24 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, and washed with methanol to obtain compound bis (4- (1H-pyrrole-1-yl) phenyl) methanone as a white solid.
The physical characteristics of the obtained bis (4- (1H-pyrrole-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; C ₆ D ₄ Cl ₂ ; δ (ppm)); 6.53-6.53 (m, 4H), 7.25-7.26 (m, 4H), 7.50 ( d, 4H), 7.98 (d, 4H)
FD-MS; 312 (M)

Synthesis Example 4-5: Synthesis of bis (4- (indoline-1-yl) phenyl) metanone (polymer modifier E4) 2.2 g (10.0 mmol) of 4,4'-difluorobenzophenone in a glass reaction vessel. ), 9.8 g (30.0 mmol) of cesium carbonate, 20 mL of dimethyl sulfoxide and 3.4 mL (30.0 mmol) of indoline were added, and the mixture was stirred at 120 ° C. for 17 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, vacuum dried, and then recrystallized from toluene to obtain compound bis (4- (indoline-1-yl) phenyl) methanone as a yellow solid.
The physical characteristics of the obtained bis (4- (indoline-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.15-3.19 (t, 4H), 4.02-4.07 (t, 4H), 6.81-6. 85 (m, 2H), 7.10-7.15 (m, 2H), 7.21-7.34 (m, 8H), 7.81-7.85 (m, 4H)
FD-MS; 416 (M)

Synthesis Example 4-6: Synthesis of bis (4- (thiazole-2-yl) phenyl) metanone (modifier F4 for polymer) In a glass reaction vessel, 3.2 mL (45.0 mmol) of tetrahydrofuran (150 mL) was placed. Cool to −75 ° C., add 30.5 mL of normal butyllithium (47.3 mmol: concentration 1.55 M / n-hexane solution), stir, and then zinc chloride 45.0 mL (45.0 mmol: concentration 1.0 M / M /). Tetrahydrofuran solution) was added, and the mixture was stirred at room temperature for 1 hour. 5.1 g (15.0 mmol) of 4,4'-dibromobenzophenone and 1.73 g (1.5 mmol) of tetrakistriphenylphosphine palladium were added, and the mixture was reacted at 55 ° C. for 17 hours. After adding methanol and quenching, the solvent was distilled off and the mixture was extracted with chloroform. The solid was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: ethyl acetate = 95: 5) was recrystallized from acetonitrile to obtain a compound bis (4- (4- (4-) Thiazol-2-yl) phenyl) methacrylate was obtained.
The physical characteristics of the obtained bis (4- (thiazole-2-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 7.48 (d, 2H), 7.88-7.94 (m, 6H), 8.11-8.14 (m, 4H)
EI-MS; 348 (M)

Synthesis Example 4-7: Synthesis of bis (4- (1H-imidazol-1-yl) phenyl) metanone (polymer modifier G4) 4.4 g (20) of 4,4'-difluorobenzophenone in a glass reaction vessel. .0 mmol), 19.6 g (60.0 mmol) of cesium carbonate, 80 mL of dimethyl sulfoxide and 3.4 g (50.0 mmol) of imidazole were added, and the mixture was stirred at 80 ° C. for 18 hours. The reaction mixture was poured into ice water, the precipitate was collected by filtration, dried under vacuum, and recrystallized from isopropyl alcohol to give the compound bis (4- (1H-imidazol-1-yl) phenyl) methanone as a white solid.
The physical characteristics of the obtained bis (4- (1H-imidazol-1-yl) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 7.21-7.22 (m, 2H), 7.43 (m, 2H), 7.56-7.60 (m, 4H), 7.93-7.98 (m, 6H)
EI-MS; 314 (M)

4-2. Production of Modified Conjugated Diene Polymer Below, reference examples relating to the production of the modified conjugated diene polymer using the above-mentioned modifier for polymer (1) will be specifically described. The polymerization conditions, modification conditions and polymerization results are summarized in Table 12.

[Measurement method of physical properties, etc.]
Since the content is the same as that described in the column of [Measurement method of physical property value] in "1-2. Production of modified conjugated diene polymer", the description thereof will be omitted.

(Example A-1B)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 475 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then 4.0 mL of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 6.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 15.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 20.0 mL of a toluene solution (0.05 mol / L) of the polymer modifier A4 was added, and the denaturation reaction was carried out at the same temperature for 15 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. Other polymerization results are shown in Table 9.

(Example A-2B)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 480 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then, 3.2 mL of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 4.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 10.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 10.0 mL of an o-dichlorobenzene solution (0.05 mol / L) of the polymer modifier B4 was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. Other polymerization results are shown in Table 9.

(Example A-3B)
The experiment was carried out in the same manner as in Example A-2B except that the amount of triethylaluminum (TEAL) was 3.1 mL and the polymer modifier B4 was changed to the polymer modifier C4. The polymerization results are shown in Table 9.

(Example A-4B)
The experiment was carried out in the same manner as in Example A-2B except that the amount of triethylaluminum (TEAL) was 3.1 mL and the polymer modifier B4 was changed to the polymer modifier D4. The polymerization results are shown in Table 9.

(Example A-5B)
The experiment was carried out in the same manner as in Example A-2B except that the amount of triethylaluminum (TEAL) was 3.1 mL and the polymer modifier B4 was changed to the polymer modifier E4. The polymerization results are shown in Table 9.

(Example A-6B)
The experiment was carried out in the same manner as in Example A-2B except that the amount of triethylaluminum (TEAL) was 3.3 mL and the polymer modifier B4 was changed to the polymer modifier F4. The polymerization results are shown in Table 9.

(Example A-7B)
The experiment was carried out in the same manner as in Example A-2B except that the amount of triethylaluminum (TEAL) was 3.1 mL and the polymer modifier B4 was changed to the polymer modifier G4. The polymerization results are shown in Table 9.

(Comparative Example A-1)
The experiment was carried out in the same manner as in Example A-2B except that the amount of triethylaluminum (TEAL) was 3.0 mL, 5 mL of an ethanol solution containing an antioxidant was added without adding a denaturing agent, and the polymerization reaction was stopped. .. The polymerization results are shown in Table 9.

Since the modified polybutadienes of Examples A-1B to A-7B have higher UV / RI values obtained by GPC analysis than the unmodified polybutadienes of Comparative Example A-1, various modifiers are bound to the polybutadienes ( It is suggested that it is denatured).

(Example B-1B)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 450 ml of cyclohexane solvent and 50 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.25 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerizing at 80 ° C. for 15 minutes, 7.5 mL of an o-dichlorobenzene solution (0.05 mol / L) of the polymer modifier B4 was added, and a denaturation reaction was carried out at 20 ° C. for 10 minutes. Next, 3 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The yield was 62.2 g / L. Other polymerization results are shown in Table 10.

(Comparative Example B-1)
Cyclohexane was 540 ml, butadiene was 60 ml, n-butyllithium was 0.20 ml, and modified polybutadiene was prepared in the same manner as in Example B-1B except that 5 ml of an ethanol solution containing an antiaging agent was added without adding a denaturant. Synthesized. The yield was 68.0 g / L. Other polymerization results are shown in Table 10.

Since the modified polybutadiene of Example B-1B has a higher UV / RI value obtained by GPC analysis than the unmodified polybutadiene of Comparative Example B-1, the modifier is bound (modified) to the polybutadiene. Is suggested.

4-3. Production of Modified Conjugated Diene Polymer Composition (Rubber Composition) (Example C-1B)
Using the modified polybutadiene of Example A-1B, using a vulcanizer, modified polybutadiene (50 parts by mass), natural rubber (50 parts by mass), carbon black (Diablack manufactured by Mitsubishi Chemical Corporation) (50 parts by mass), zinc oxide (50 parts by mass). 3 parts by mass), stearic acid (2 parts by mass), anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) (2 parts by mass), oil (Viva Tech 400 manufactured by H & R) (3 parts by mass) and knead. Perform the primary compounding, and then perform the secondary compounding by adding the vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) (1 part by mass) and sulfur (1.5 parts by mass) by roll. Then, a compounded rubber was produced. Further, this compounded rubber was molded according to the target physical characteristics, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured. Table 11 shows the results of measuring the physical characteristics of various formulations.

(Example C-2B)
A compounded rubber was prepared in the same manner as in Example C-1B except that the modified polybutadiene of Example A-2B was used instead of the modified polybutadiene of Example A-1B, and the vulcanized product was molded and press vulcanized. Physical properties were measured. Table 11 shows the measurement of the physical characteristics of various formulations.

(Example C-3B)
A compounded rubber was prepared in the same manner as in Example C-1B except that the modified polybutadiene of Example A-3B was used instead of the modified polybutadiene of Example A-1B, and the vulcanized product was molded and press vulcanized. Physical properties were measured. Table 11 shows the measurement of the physical characteristics of various formulations.

(Example C-4B)
A compounded rubber was prepared in the same manner as in Example C-1B except that the modified polybutadiene of Example A-4B was used instead of the modified polybutadiene of Example A-1B, and the vulcanized product was molded and press vulcanized. Physical properties were measured. Table 11 shows the measurement of the physical characteristics of various formulations.

(Example C-5B)
A compounded rubber was prepared in the same manner as in Example C-1B except that the modified polybutadiene of Example A-5B was used instead of the modified polybutadiene of Example A-1B, and the vulcanized product was molded and press vulcanized. Physical properties were measured. Table 11 shows the measurement of the physical characteristics of various formulations.

(Example C-6B)
A compounded rubber was prepared in the same manner as in Example C-1B except that the modified polybutadiene of Example A-6B was used instead of the modified polybutadiene of Example A-1B, and the vulcanized product was molded and press vulcanized. Physical properties were measured. Table 11 shows the measurement of the physical characteristics of various formulations.

(Comparative Example C-1)
Formulated in the same manner as in Reference Example C-1B except that JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene of Reference Example A-1B. Rubber was prepared, molded, and press-vulcanized to measure the physical properties of the vulcanized product. Table 11 shows the results of measuring the physical characteristics of various formulations.

The numerical values in Table 11 are each item when each characteristic value of Comparative Example C-1 using JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation is used as a reference (100). Each is displayed in exponential notation. The larger the value, the better the characteristics.

As shown in Table 11, the compositions of Examples C-1B to C-6B using the modified polybutadienes obtained in Examples A-1B to A-6B are JSR BR01 (using a Ni-based catalyst). It is superior in tensile stress, rebound resilience, abrasion resistance, and fuel efficiency (tan δ) to the composition of Comparative Example C-1 using polymerized polybutadiene).

5-1. Polymer modifiers (1) "(A ¹ and A ^{2 in} formula (1) are 6-membered ring aromatic heterocyclic groups containing at least one nitrogen atom as a ring constituent element, and are R ¹ and R ^2". Is a compound that is an unsaturated 3- to 12-membered ring heterocyclic group) ”and a polymer modifier (2)“ Classification (3) ” Described in.

[Synthesis Example 5-1] Synthesis of Bis (6- (Methyl (Phenyl) Amino) Pyridine-3-yl) Metanone (Modifier A5 for Polymer) Synthesis of Bis (6-Bromopyridine-3-yl) Methanol )
Put 250 mL of tetrahydrofuran in a glass reaction vessel, cool to -75 ° C, 11.3 mL of n-butyllithium (17.5 mmol: concentration 1.55 M / n-hexane solution), 8.8 mL of n-butylmagnesium chloride (8). .75 mmol: concentration 1.0 M / tetrahydrofuran solution) was added to bring it to −10 ° C., then cooled to −75 ° C. again, and 2-bromo-5-iodopyridine was added to bring it to −15 ° C. The mixture was cooled to −75 ° C. again, 6-bromo-3-pyridinecarboxyaldehyde was added, and the mixture was reacted overnight at room temperature. Then, saturated ammonium chloride chloride and chloroform were added to separate the organic layer, dried with magnesium sulfate, the solvent was distilled off under reduced pressure, and the compound was purified by silica gel column chromatography (chloroform: ethyl acetate = 9: 1) to form a compound as a white solid. Bis (6-bromopyridine-3-yl) methanol was obtained.
The physical characteristics of the obtained bis (6-bromopyridin-3-yl) methanol were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.21 (d, 1H), 5.88 (d, 1H), 7.33-7.60 (m, 4H), 8 .35 (s, 2H)
EI-MS; 344 (M)

(Synthesis of bis (6-bromopyridin-3-yl) metanone)
In a glass reaction vessel, 15.6 g (45.2 mmol) of bis (6-bromopyridin-3-yl) methanol obtained above, 150 mL of acetonitrile, 18.1 g (29.4 mmol) of potassium peroxymonosulfate, 2- 152.1 mg (0.45 mmol) of potassium iodo-5-methylbenzenesulfonate was added and reacted at 70 ° C. Chloroform was added, the insoluble material was filtered off, and the solvent was distilled off under reduced pressure. The obtained yellow solid was purified by silica gel column chromatography (chloroform), and the compound bis (6-bromopyridine-3-yl) was obtained as a white solid. Obtained Metanon.
The physical characteristics of the obtained bis (6-bromopyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 7.68-7.71 (m, 2H), 7.96-7.98 (m, 2H), 8.71-8. 72 (m, 2H)
EI-MS; 341 (M)

(Synthesis of Bis (6- (Methyl (Phenyl) Amino) Pyridine-3-yl) Metanone)
In a glass reaction vessel, 5.1 g (15.0 mmol) of bis (6-bromopyridin-3-yl) methanone obtained above, 4.3 g (45.0 mmol) of sodium tert-butoxide, 2-dicyclohexylphosphino -2.46 g (6.0 mmol) of -2', 6'-dimethoxybiphenyl, 1.37 g (1.5 mmol) of tris (dibenzylideneacetone) dipalladium, 150 mL of toluene, 4.1 mL (37.5 mmol) of N-methylaniline Was put in and reacted overnight at room temperature. A saturated aqueous solution of ammonium chloride chloride was added, the mixture was extracted with ethyl acetate, dried over magnesium sulfate, the solvent was evaporated under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: ethyl acetate = 97: 3) was reconstituted from diisopropyl ether. Crystallization gave the compound bis (6- (methyl (phenyl) amino) pyridine-3-yl) metanone as a yellow solid.
The physical characteristics of the obtained bis (6- (methyl (phenyl) amino) pyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.53 (s, 6H), 6.48-6.50 (m, 2H), 7.29-7.33 (m, 6H), 7.44-7.47 (m, 4H), 7.75-7.78 (m, 2H), 8.61-8.62 (m, 2H)
EI-MS; 394 (M)

[Synthesis Example 5-2] Synthesis of bis (6- (1-methyl-1H-imidazol-2-yl) pyridine-3-yl) metanone (modifier B5 for polymer) 1-methyl in a glass reaction vessel. Add 3.6 mL (45.0 mmol) tetrahydrofuran (150 mL) of imidazole, cool to −75 ° C., add 30.3 mL (47.3 mmol: concentration 1.55 M / n-hexane solution) of n-butyllithium, and add 1 at the same temperature. After stirring for hours, 45.0 mL of zinc chloride (45.0 mmol: concentration 1.0 M / tetrahydrofuran solution) was added, and then the mixture was stirred at room temperature for 1 hour. 5.1 g (15.0 mmol) of bis (6-bromopyridin-3-yl) methanone obtained in the same manner as in Synthesis Example 1 and 1.73 g (1.5 mmol) of tetrakistriphenylphosphine palladium were added, and the temperature was 55 ° C. Allowed to react overnight. After adding methanol and quenching, the solvent was distilled off and the mixture was extracted with chloroform. The solid was dried with magnesium sulfate, the solvent was distilled off under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: normal hexane = 7: 3) was recrystallized from acetonitrile to form a pale yellow solid with compound bis (6- (1). -Methyl-1H-imidazol-2-yl) pyridine-3-yl) metanone was obtained.
The physical characteristics of the obtained bis (6- (1-methyl-1H-imidazol-2-yl) pyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 4.16 (s, 6H), 7.07 (d, 2H), 7.14 (d, 2H), 8.17-8 .20 (m, 2H), 8.35-8.37 (m, 2H), 8.99-9.00 (m, 2H)
EI-MS; 344 (M)

[Synthesis Example 5-3] Synthesis of Bis (6- (Methyl (Pyridine-2-yl) Amino) Pyridine-3-yl) Metanone (Modifier C5 for Polymers) In a glass reaction vessel, the above Synthesis Example 1 and Similarly obtained bis (6-bromopyridin-3-yl) methanone 5.1 g (15.0 mmol), sodium tert-butoxide 4.3 g (45.0 mmol), 2- (dicyclohexylphosphino) biphenyl 895.2 mg (3.0 mmol), tris (dibenzilidenacetone) dipalladium 686.8 mg (0.75 mmol), toluene 150 mL, 2- (methylamino) pyridine 3.8 mL (37.5 mmol) were added, and the mixture was reacted overnight at room temperature. .. A saturated aqueous solution of ammonium chloride chloride was added, the mixture was extracted with ethyl acetate, dried with magnesium sulfate, the solvent was evaporated under reduced pressure, and the solid purified by silica gel column chromatography (chloroform: ethyl acetate = 8: 2) was recrystallized from acetonitrile. As a result, the compound bis (6- (methyl (pyridine-2-yl) amino) pyridine-3-yl) metanone was obtained as a pale yellow solid.
The physical characteristics of the obtained bis (6- (methyl (pyridin-2-yl) amino) pyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.66 (s, 6H), 7.06-7.14 (m, 4H), 7.34-7.37 (m, 2H), 7.68-7.70 (m, 2H), 7.93-7.96 (m, 2H), 8.43-8.45 (m, 2H), 8.69-8.70 ( m, 2H)
EI-MS; 396 (M)

[Synthesis Example 5-4] Synthesis of Bis (6- (Di (Pyridine-2-yl) Amino) Pyridine-3-yl) Metanone (Modifier D5 for Polymers) In a glass reaction vessel, the above Synthesis Example 1 and 2.4 g (7.0 mmol) of bis (6-bromopyridin-3-yl) metanone obtained in the same manner, 2.0 g (21.0 mmol) of sodium tert-butoxide, 2-dicyclohexylphosphino-2', 6'. Add 1.15 g (2.8 mmol) of -dimethoxybiphenyl, 641 mg (0.7 mmol) of tris (dibenzilidenacetone) dipalladium, 140 mL of toluene, and 3.0 g (17.5 mmol) of 2,2'-dipyridylamine, and add 70 ° C. Reacted with. Saturated ammonium chloride chloride aqueous solution is added, extracted with ethyl acetate, dried with magnesium sulfate, the solvent is distilled off under reduced pressure, and purification is performed by silica gel column chromatography (chloroform: normal hexane = 7: 3) to obtain a yellow solid. The compound bis (6- (di (pyridine-2-yl) amino) pyridine-3-yl) metanone was obtained.
The physical characteristics of the obtained bis (6- (di (pyridin-2-yl) amino) pyridin-3-yl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 7.15-7.17 (m, 10H), 7.70-7.74 (m, 4H), 8.02-8. 05 (m, 2H), 8.39-8.41 (m, 4H), 8.66-8.68 (m, 2H)
FD-MS; 522 (M)

5-2. Production of Modified Conjugated Diene Polymer Below, reference examples relating to the production of the modified conjugated diene polymer using the above-mentioned modifiers (1) and (2) for the polymer will be specifically described. The polymerization conditions, modification conditions and polymerization results are summarized in Table 16.

[Measurement method of physical properties, etc.]
Since the content is the same as that described in the column of [Measurement method of physical property value] in "1-2. Production of modified conjugated diene polymer", the description thereof will be omitted.

(Reference Example A-1C)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 480 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then, 3.2 mL of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 4.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 10.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 10.0 mL of a toluene solution (0.05 mol / L) of the polymer modifier A5 was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. Other polymerization results are shown in Table 12.

(Example A-2C)
The experiment was carried out in the same manner as in Reference Example A-1C except that the amount of triethylaluminum (TEAL) was 3.8 mL and the polymer modifier A5 was changed to the polymer modifier B5. The polymerization results are shown in Table 12.

(Reference Example A-3C)
The experiment was carried out in the same manner as in Reference Example A-1C except that the amount of triethylaluminum (TEAL) was 3.5 mL and the polymer modifier A5 was changed to the polymer modifier C5. The polymerization results are shown in Table 12.

(Reference Example A-4C)
The experiment was carried out in the same manner as in Reference Example A-1C except that the amount of triethylaluminum (TEAL) was 3.5 mL and the polymer modifier A5 was changed to the polymer modifier D5. The polymerization results are shown in Table 12.

(Comparative Example A-1)
Experiments were carried out in the same manner as in Reference Example A-1C, except that triethylaluminum (TEAL) was adjusted to 3.0 mL, 5 mL of an ethanol solution containing an antioxidant was added without adding a denaturing agent, and the polymerization reaction was stopped. rice field. The polymerization results are shown in Table 12.

Since the modified polybutadienes of Reference Examples A-1C to A-3C have a larger UV / RI value obtained by GPC analysis than the unmodified polybutadienes of Comparative Example A-1, various modifiers are bound to the polybutadienes. It is suggested that it is (denatured).

(Reference Example B-1C)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 450 ml of cyclohexane solvent and 50 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.25 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerizing at 80 ° C. for 15 minutes, 7.5 mL of a toluene solution (0.05 mol / L) of the polymer modifier A5 was added, and a denaturation reaction was carried out at 20 ° C. for 10 minutes. Next, 3 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The yield was 59.3 g / L. Other polymerization results are shown in Table 13.

(Example B-2C)
The experiment was carried out in the same manner as in Reference Example B-1C except that n-butyllithium was 0.28 ml and the polymer modifier A5 was changed to the polymer modifier B5. The yield was 63.7 g / L. Other polymerization results are shown in Table 13.

(Reference Example B-3C)
The experiment was carried out in the same manner as in Reference Example B-1C except that the polymer modifier A5 was changed to the polymer modifier C5. The yield was 64.9 g / L. Other polymerization results are shown in Table 13.

(Reference Example B-4C)
The experiment was carried out in the same manner as in Reference Example B-1C except that n-butyllithium was adjusted to 0.20 ml, the polymer modifier A5 was changed to the polymer modifier D5, and the modification reaction was carried out at 80 ° C. for 10 minutes. went. The yield was 64.5 g / L. Other polymerization results are shown in Table 13.

(Comparative Example B-1)
Cyclohexane was 540 ml, butadiene was 60 ml, n-butyllithium was 0.20 ml, and 5 ml of an ethanol solution containing an antiaging agent was added without adding a denaturing agent, in the same manner as in Reference Example B-1C. Modified polybutadiene was synthesized. The yield was 68.0 g / L. Other polymerization results are shown in Table 13.

Since the modified polybutadiene of Reference Examples B-1C, B-3C, B-4C and Example B-2C has a larger UV / RI value obtained by GPC analysis than the unmodified polybutadiene of Comparative Example B-1, It is suggested that the denaturant is bound (modified) to polybutadiene.

5-3. Production of Modified Conjugated Diene Polymer Composition (Rubber Composition) (Reference Example C-1C)
Reference Example Using modified polybutadiene of A-1C, modified polybutadiene (50 parts by mass), natural rubber (50 parts by mass), carbon black (dia black manufactured by Mitsubishi Chemical Co., Ltd.) (50 parts by mass), zinc oxide by vulcanization. Add (3 parts by mass), stearic acid (2 parts by mass), anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) (2 parts by mass), and oil (Viva Tech 400 manufactured by H & R) (3 parts by mass) and knead. The primary formulation is carried out, and then the secondary formulation is carried out by adding a vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) (1 part by mass) and sulfur (1.5 parts by mass) on a roll. As a result, a compounded rubber was produced. Further, this compounded rubber was molded according to the target physical characteristics, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured. Table 14 shows the results of measuring the physical characteristics of various formulations.

(Example C-2C)
A compounded rubber was prepared in the same manner as in Reference Example C-1C except that modified polybutadiene synthesized according to Example A-2C was used instead of the modified polybutadiene of Reference Example A-1C, and molded and press vulcanized. The physical properties of the vulcanized product were measured. Table 14 shows the results of measuring the physical characteristics of various formulations.

(Reference Example C-3C)
A compounded rubber was prepared in the same manner as in Reference Example C-1C except that modified polybutadiene synthesized according to Reference Example A-3C was used instead of the modified polybutadiene of Reference Example A-1C, and molded and press vulcanized. The physical properties of the vulcanized product were measured. Table 14 shows the results of measuring the physical characteristics of various formulations.

(Comparative Example C-1)
Formulated in the same manner as in Reference Example C-1C except that JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene of Reference Example A-1C. Rubber was prepared, molded, and press-vulcanized to measure the physical properties of the vulcanized product. Table 14 shows the results of measuring the physical characteristics of various formulations.

The numerical values in Table 14 are each item when each characteristic value of Comparative Example C-1 using JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation is used as a reference (100). Each is displayed in exponential notation. The larger the value, the better the characteristics.

As shown in Table 14, the compositions of Reference Examples C-1C, C-3C and Example C-2C using the modified polybutadiene obtained by Reference Examples A-1C, A-3C and Example A-2C are , JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) is superior to the composition of Comparative Example C-1 in tensile stress, abrasion resistance, and fuel efficiency (tan δ).

6-1. Polymer modifiers (2) Synthesis examples of "Classification (4)" The synthesis examples of polymer modifiers will be specifically described below.

Synthesis Example 6-1: Synthesis of bis (4- (methyl (phenyl) amino) phenyl) metanone (polymer modifier A6) 5.1 g (15.0 mmol) of 4,4'-dibromobenzophenone in a glass reaction vessel. ), Sodium tert-butoxide 4.3 g (45.0 mmol), 2- (dicyclohexylphosphino) biphenyl 895.2 mg (3.0 mmol), tris (dibenzylideneacetone) dipalladium 686.8 mg (0.75 mmol), toluene 150 mL and 4.1 mL (37.5 mmol) of N-methylaniline were added and reacted overnight at room temperature. A saturated aqueous solution of ammonium chloride chloride was added, extracted with ethyl acetate, dried with magnesium sulfate, the solvent was distilled off under reduced pressure, and a solid purified by silica gel column chromatography (normal hexane: ethyl acetate = 85: 15) was obtained from dibutyl ether. By recrystallization, the compound bis (4- (methyl (phenyl) amino) phenyl) metanone was obtained as a pale yellow solid.
The physical characteristics of the obtained bis (4- (methyl (phenyl) amino) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.38 (s, 6H), 6.80-6.83 (m, 4H), 7.17-7.25 (m, 6H), 7.37-7.43 (m, 4H), 7.63-7.67 (m, 4H)
EI-MS; 392 (M)

Synthesis Example 6-2: Synthesis of bis (4- (methyl (pyridin-2-yl) amino) phenyl) metanone (modifier for polymer B6) 4,4'-dibromobenzophenone 510.0 mg in a glass reaction vessel (1.5 mmol), sodium tert-butoxide 432 mg (4.5 mmol), 2- (dicyclohexylphosphino) biphenyl 89.5 mg (0.3 mmol), tris (dibenzylideneacetone) dipalladium 68.7 mg (0.075 mmol) , 15 mL of toluene and 383 μL (3.75 mmol) of 2- (methylamino) pyridine were added and reacted overnight at room temperature. A saturated aqueous solution of ammonium chloride chloride was added, the mixture was extracted with ethyl acetate, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the solid was purified by silica gel column chromatography (normal hexane: ethyl acetate = 85: 15-65: 35). Was recrystallized from methyl alcohol to give the compound bis (4- (methyl (pyridine-2-yl) amino) phenyl) methanol as a white solid.
The physical characteristics of the obtained bis (4- (methyl (pyridine-2-yl) amino) phenyl) methanone were as follows.
^{1 1} H-NMR (400 MHz; CD ₂ Cl ₂ ; δ (ppm)); 3.55 (s, 6H), 6.77-6.80 (m, 2H), 6.93-6.96 (m, 2H), 7.30-7.34 (m, 4H), 7.46-7.51 (m, 2H), 7.79-7.83 (m, 4H), 8.27-8.29 ( m, 2H)
EI-MS; 394 (M)

6-2. Production of Modified Conjugated Diene Polymer The following specifically describes a reference example relating to the production of a modified conjugated diene polymer using the above-mentioned modifier for polymer (2). The polymerization conditions, modification conditions and polymerization results are summarized in Table 20.

[Measurement method of physical properties, etc.]
Since the content is the same as that described in the column of [Measurement method of physical property value] in "1-2. Production of modified conjugated diene polymer", the description thereof will be omitted.
(Reference Example A-1D)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 480 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then 3.3 mL of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 4.0 mL of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) _{3) was added, and then triphenyl.} 10.0 mL of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 10.0 mL of a toluene solution (0.05 mol / L) of the polymer modifier A6 was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. Next, 5 mL of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. Other polymerization results are shown in Table 15.

(Reference Example A-2D)
The same experiment as in Reference Example A-1D was carried out except that the cyclohexane solution of triethylaluminum (TEAL) was adjusted to 3.2 mL and the polymer modifier A6 was changed to the polymer modifier B6. The polymerization results are shown in Table 15.

(Comparative Example A-1)
Experiments were carried out in the same manner as in Reference Example A-1D, except that triethylaluminum (TEAL) was adjusted to 3.0 mL, 5 mL of an ethanol solution containing an antiaging agent was added without adding a denaturing agent, and the polymerization reaction was stopped. rice field. The polymerization results are shown in Table 15.

Since the modified polybutadienes of Reference Examples A-1D to A-2D have a larger UV / RI value obtained by GPC analysis than the unmodified polybutadienes of Comparative Example A-1, various modifiers are bound to the polybutadienes. It is suggested that it is (denatured).

(Reference Example B-1D)
The inside of the autoclave was replaced with nitrogen, and a solution consisting of 450 ml of cyclohexane solvent and 50 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.25 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerizing at 80 ° C. for 15 minutes, 7.5 mL of a toluene solution (0.05 mol / L) of the polymer modifier A6 was added, and a denaturation reaction was carried out at 20 ° C. for 10 minutes. Next, 3 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The yield was 55.1 g / L. Other polymerization results are shown in Table 16.

(Reference Example B-2D)
The experiment was carried out in the same manner as in Reference Example B-1D except that the polymer modifier A6 was changed to the polymer modifier B6. The yield was 60.4 g / L. Other polymerization results are shown in Table 16.

(Comparative Example B-1)
The experiment was carried out in the same manner as in Reference Example B-1D, except that n-butyllithium was 0.20 ml and 5 ml of an ethanol solution containing an antiaging agent was added without adding a denaturing agent. The yield was 68.0 g / L. Other polymerization results are shown in Table 16.

Since the modified polybutadienes of Reference Examples B-1D and B-2D have higher UV / RI values obtained by GPC analysis than the unmodified polybutadienes of Comparative Example B-1, the modifier is bound to the polybutadienes ( It is suggested that it is denatured).

3. 3. Production of Modified Conjugated Diene Polymer Composition (Rubber Composition) (Reference Example C-1D)
Reference Example Using the modified polybutadiene of A-1D, modified polybutadiene (50 parts by mass), natural rubber (50 parts by mass), carbon black (Diablack manufactured by Mitsubishi Chemical Corporation) (50 parts by mass), zinc oxide by vulcanization. (3 parts by mass), stearic acid (2 parts by mass), anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) (2 parts by mass), oil (Viva Tec 400 manufactured by H & R) (3 parts by mass) are added and kneaded. The primary formulation is carried out, and then the secondary formulation is carried out by adding a vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) (1 part by mass) and sulfur (1.5 parts by mass) on a roll. As a result, a compounded rubber was produced. Further, this compounded rubber was molded according to the target physical characteristics, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured. Table 17 shows the results of measuring the physical characteristics of various formulations.

(Reference Example C-2D)
A compounded rubber was prepared in the same manner as in Reference Example C-1D except that the modified polybutadiene of Reference Example A-2D was used instead of the modified polybutadiene of Reference Example A-1D, and was molded and press-vulcanized. The physical properties of the vulcanized product were measured. Table 17 shows the results of measuring the physical characteristics of various formulations.

(Comparative Example C-1)
Formulated in the same manner as in Reference Example C-1D except that JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene of Reference Example A-1D. Rubber was prepared, molded, and press-vulcanized to measure the physical properties of the vulcanized product. Table 17 shows the results of measuring the physical characteristics of various formulations.

The numerical values in Table 17 are each item when each characteristic value of Comparative Example C-1 using JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation is used as a reference (100). Each is displayed in exponential notation. The larger the value, the better the characteristics.

As shown in Table 17, the compositions of Reference Example C-1D and Reference Example C-2D using the modified polybutadiene obtained by Reference Example A-1D and Reference Example A-2D are JSR BR01 (Ni-based). It is superior in tensile stress, breaking strength, rebound resilience, abrasion resistance, and fuel efficiency (tan δ) to the composition of Comparative Example C-1 using (polybutadiene polymerized using a catalyst).

（Ｚは酸素原子又は硫黄原子を示す。
Ａ^１及びＡ^２は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す。
Ｒ^１及びＲ^２は、Ａ^１及びＡ^２の炭素原子と結合しており、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を複素環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を複素環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に１〜４の整数で、ｍ＋ｎ≧２を満たす数値である。）
［２］前記式（１）のｍ及びｎが１である、請求項１に記載の重合体用変性剤。
［３］前記式（１）のＲ^１及びＲ^２中の複素環の窒素原子がＡ^１及びＡ^２の炭素原子と結合している、［１］又は［２］の重合体用変性剤。
［４］前記式（１）のＲ^１及びＲ^２がＡ^１及びＡ^２のパラ位の炭素原子と結合している、［１］〜［３］の重合体用変性剤。
［５］前記式（１）のＲ^１及びＲ^２は、各々独立に、窒素原子１又は２個を環の構成成分に含む飽和又は不飽和の５〜６員環複素環基、窒素原子１個と酸素原子１個を環の構成成分に含む飽和又は不飽和の５〜６員環複素環基及び窒素原子１個と硫黄原子１個を環の構成成分に含む飽和又は不飽和の５〜６員環複素環基からなる群より選ばれる複素環基である、［１］〜［４］の重合体用変性剤。
［６］下記の一般式（１）で表される化合物を含む、重合体用変性剤。

（Ｚは酸素原子又は硫黄原子を示す。
Ａ ^１ 及びＡ ^２ は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す。
Ｒ ^１ 及びＲ ^２ は、Ａ ^１ 及びＡ ^２ の炭素原子と結合しており、各々独立に、無置換又は置換基を有するピロリジル基、ピペリジル基、ピペラジル基、チアゾリジル基及びチオモルホリル基からなる群より選ばれる飽和の複素環基及びチアゾリル基及びピロリル基からなる群より選ばれる不飽和の複素環基である。
ｍ及びｎは、ｍ＝１、ｎ＝０である。）
［７］前記式（１）のＲ^１及びＲ^２は、各々独立に、無置換又は置換基を有し、置換基は各々独立に、炭素数１〜１２の直鎖状又は分岐状のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜６の直鎖状又は分岐状のハロゲン化アルキル基、炭素数1〜１２の直鎖状又は分岐状のアルキル基で置換されたアミノ基、窒素原子を１個以上含む３〜１２員環複素環基、炭素数１〜６のアルコキシ基及びアリール基からなる群より選択される置換基である、［１］〜［６］の重合体用変性剤。
［８］希土類金属化合物及び／又はアルカリ金属化合物を用いて共役ジエン化合物を重合させて共役ジエン重合体を得る工程と、
前記共役ジエン重合体と［１］〜［７］の重合体用変性剤とを反応させて変性共役ジエン重合体を得る工程と、を有する、変性共役ジエン重合体の製造方法。
［９］前記希土類金属化合物は、下記の一般式（７）で表される非メタロセン型金属化合物である、［８］の変性共役ジエン重合体の製造方法。

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the heterocycle, and one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the heterocycle.
m and n are each independently an integer of 1 to 4, and are numerical values satisfying m + n ≧ 2. )
[2] The modifier for a polymer according to claim 1, wherein m and n of the formula (1) are 1.
[3] The polymer modifier of [1] or [2], wherein the nitrogen atom of the heterocycle in ^{R 1} and R ² of the above formula (1) ^{is bonded to the carbon atom of A 1} and A ^2.
[4] The polymer modifier of [1] to [3], ^{wherein R 1} and R ² of the above formula (1) are bonded to carbon atoms at the para positions of A ¹ and A ^{2.
[5] R 1} and R ² of the above formula (1) are saturated or unsaturated 5- to 6-membered ring heterocyclic groups containing 1 or 2 nitrogen atoms as ring constituents, and nitrogen atom 1 respectively. Saturated or unsaturated 5- to 6-membered heterocyclic groups containing one and one oxygen atom in the ring constituents and saturated or unsaturated 5- to six-membered ring heterocyclic groups containing one nitrogen atom and one sulfur atom in the ring constituents. The modifiers for polymers [1] to [4], which are heterocyclic groups selected from the group consisting of 6-membered heterocyclic groups.
[6] A polymer modifier containing a compound represented by the following general formula (1).

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² consist of a group consisting of a pyrrolidyl group, a piperidyl group, a piperazyl group, a thiazolizyl group and a thiomorpholyl group, each of which is bonded to the carbon atoms of A ¹ and A ^{2 and has an unsaturated or substituent, respectively.} It is an unsaturated heterocyclic group selected from the group consisting of a selected saturated heterocyclic group and a thiazolyl group and a pyrrolyl group.
m and n are m = 1 and n = 0. )
[ 7 ^{] R 1} and R ² of the above formula (1) each independently have an unsubstituted or substituent, and each of the substituents independently has a linear or branched alkyl having 1 to 12 carbon atoms. Amino substituted with a group, a cycloalkyl group having 3 to 12 carbon atoms, a linear or branched alkyl halide group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 12 carbon atoms. The weight of [1] to [6 ], which is a substituent selected from the group consisting of a group, a 3- to 12-membered ring heterocyclic group containing one or more nitrogen atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group. Denaturer for coalescence.
[ 8 ] A step of polymerizing a conjugated diene compound using a rare earth metal compound and / or an alkali metal compound to obtain a conjugated diene polymer.
A method for producing a modified conjugated diene polymer, which comprises a step of reacting the conjugated diene polymer with the modifiers for polymers [1] to [ 7] to obtain a modified conjugated diene polymer.
[ 9 ] The method for producing a modified conjugated diene polymer according to [8 ], wherein the rare earth metal compound is a non-metallocene type metal compound represented by the following general formula (7).

（但し、Ｒ^３、Ｒ^５は炭素数１〜１２の炭化水素基を表し、Ｒ^４は水素又は炭素数１〜１２の炭化水素基を表し、Ｏは酸素原子を表し、Ｍは希土類金属原子を表す。）
。
［１０］［８］又は［９］の変性共役ジエン重合体の製造方法により製造される、変性共役ジエン重合体。
［１１］共役ジエン重合体の末端に下記一般式（１）で示される化合物由来の構造を有する変性共役ジエン重合体。

(However, R ³ and R ⁵ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁴ represents hydrogen or hydrocarbon groups having 1 to 12 carbon atoms, O represents an oxygen atom, and M represents a rare earth metal atom. Represents.)
..
[ 10 ] A modified conjugated diene polymer produced by the method for producing a modified conjugated diene polymer according to [8] or [9].
[ 11 ] A modified conjugated diene polymer having a structure derived from a compound represented by the following general formula (1) at the end of the conjugated diene polymer.

（Ｚは酸素原子又は硫黄原子を示す。
Ａ ^１ 及びＡ ^２ は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す。
Ｒ^１及びＲ^２は、Ａ^１及びＡ^２の炭素原子と結合しており、各々独立に、無置換又は置換基を有する飽和又は不飽和の３〜１２員環複素環基であり、窒素原子１個を環の構成元素に含み、窒素原子、酸素原子及び硫黄原子からなる群から選択される１個のヘテロ原子を環の構成成分として更に含んでもよい。
ｍ及びｎは、各々独立に１〜４の整数で、ｍ＋ｎ≧２を満たす数値である。）
［１２］共役ジエン重合体の末端に下記一般式（１）で示される化合物由来の構造を有する変性共役ジエン重合体。

（Ｚは酸素原子又は硫黄原子を示す。
Ａ ^１ 及びＡ ^２ は、６員環芳香環基又は少なくとも窒素原子１個を環の構成元素に含む６員環芳香族複素環基を示す。
Ｒ ^１ 及びＲ ^２ は、Ａ ^１ 及びＡ ^２ の炭素原子と結合しており、各々独立に、無置換又は置換基を有するピロリジル基、ピペリジル基、ピペラジル基、チアゾリジル基及びチオモルホリル基からなる群より選ばれる飽和の複素環基及びチアゾリル基及びピロリル基からなる群より選ばれる不飽和の複素環基である。
ｍ及びｎは、ｍ＝１、ｎ＝０である。）
［１３］［１０］〜［１２］の変性共役ジエン重合体を含む、ゴム組成物。
［１４］［１３］のゴム組成物を用いたタイヤ。
［１５］［１３］のゴム組成物を用いたゴムベルト。

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the ring, and one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the ring.
m and n are each independently an integer of 1 to 4, and are numerical values satisfying m + n ≧ 2. )
[12] A modified conjugated diene polymer having a structure derived from a compound represented by the following general formula (1) at the end of the conjugated diene polymer.

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² consist of a group consisting of a pyrrolidyl group, a piperidyl group, a piperazyl group, a thiazolizyl group and a thiomorpholyl group, each of which is bonded to the carbon atoms of A ¹ and A ^{2 and has an unsaturated or substituent, respectively.} It is an unsaturated heterocyclic group selected from the group consisting of a selected saturated heterocyclic group and a thiazolyl group and a pyrrolyl group.
m and n are m = 1 and n = 0. )
A rubber composition containing the modified conjugated diene polymers of [13 ] [ 10 ] to [ 12].
A tire using the rubber composition of [ 14 ] and [ 13].
A rubber belt using the rubber composition of [ 15 ] and [ 13].

Claims (13)

A modifier for a polymer, which comprises a compound represented by the following general formula (1).

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the heterocycle, and one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the heterocycle.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. ) The polymer modifier according to claim 1, wherein m and n of the formula (1) are 1. The polymer modifier according to claim 1 or 2, wherein the nitrogen atom of the heterocycle in ^{R 1} and R ² of the formula (1) ^{is bonded to the carbon atom of A 1} and A ^2. The polymer modifier according to any one of claims 1 to 3, ^{wherein R 1} and R ² of the formula (1) are bonded to a carbon atom at the para position of A ¹ and A ^{2. R 1} and R ² of the above formula (1) are each independently a saturated or unsaturated 5- to 6-membered ring heterocyclic group containing 1 or 2 nitrogen atoms in the ring constituents, 1 nitrogen atom and oxygen. Saturated or unsaturated 5- to 6-membered ring heterocyclic group containing one atom as a constituent of the ring and a saturated or unsaturated 5- to 6-membered ring containing one nitrogen atom and one sulfur atom as constituents of the ring. The modifier for a polymer according to any one of claims 1 to 4, which is a heterocyclic group selected from the group consisting of heterocyclic groups. ^{R 1} and R ² of the above formula (1) each independently have an unsubstituted or substituent, and each of the substituents independently has a linear or branched alkyl group having 1 to 12 carbon atoms, carbon. Cycloalkyl group of number 3 to 12, linear or branched alkyl halide group of 1 to 6 carbons, amino group substituted with linear or branched alkyl group of 1 to 12 carbons, nitrogen The claim 1 to any one of claims 1 to 5, which is a substituent selected from the group consisting of a 3- to 12-membered ring heterocyclic group containing one or more atoms, an alkoxy group having 1 to 6 carbon atoms and an aryl group. Modulator for polymers. A step of polymerizing a conjugated diene compound using a rare earth metal compound and / or an alkali metal compound to obtain a conjugated diene polymer, and
A method for producing a modified conjugated diene polymer, which comprises a step of reacting the conjugated diene polymer with the modifier for polymer according to any one of claims 1 to 6 to obtain a modified conjugated diene polymer. .. The method for producing a modified conjugated diene polymer according to claim 7, wherein the rare earth metal compound is a non-metallocene type metal compound represented by the following general formula (6).

(However, R ³ and R ⁵ represent hydrocarbon groups having 1 to 12 carbon atoms, R ⁴ represents hydrogen or hydrocarbon groups having 1 to 12 carbon atoms, O represents an oxygen atom, and M represents a rare earth metal atom. Represents.)
.. A modified conjugated diene polymer produced by the method for producing a modified conjugated diene polymer according to claim 7 or 8. A modified conjugated diene polymer having a structure derived from a compound represented by the following general formula (1) at the end of the conjugated diene polymer.

(Z represents an oxygen atom or a sulfur atom.
A ¹ and A ² represent a 6-membered ring aromatic heterocyclic group containing a 6-membered ring aromatic ring group or at least one nitrogen atom as a constituent element of the ring.
R ¹ and R ² are saturated or unsaturated 3- to 12-membered heterocyclic groups bonded to the carbon atoms of ^{A 1} and A ^{2 and each independently having an unsubstituted or substituent, and a nitrogen atom.} One may be contained as a constituent element of the ring, and one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom may be further contained as a constituent element of the ring.
m and n are each independently an integer of 0 to 4, and are numerical values satisfying m + n ≧ 1. ) A rubber composition comprising the modified conjugated diene polymer according to claim 9 or 10. A tire using the rubber composition according to claim 11. A rubber belt using the rubber composition according to claim 11.