JP2013028781A - Method for producing conjugated dienic polymer, conjugated dienic polymer, and conjugated dienic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a conjugated dienic polymer, capable of providing a polymer composition excellent in fuel consumption saving.SOLUTION: The method for producing a conjugated dienic polymer includes: adding the following compounds (I) and (II) as polymerization initiator components in this order to a solution containing at least one monomer component in a hydrocarbon as a solvent; and polymerizing the monomer component containing a conjugated diene compound and a silicon-containing vinyl compound. (I): an organic alkaline metal compound. (II): a compound represented by formula (1), wherein Ris a 3-20C hydrocarbylene group which may have, as a heteroatom, at least one atom selected from the atom group consisting of a silicon atom, a nitrogen atom and an oxygen atom.

Description

  The present invention relates to a method for producing a conjugated diene polymer, a conjugated diene polymer, and a conjugated diene polymer composition.

  In recent years, due to increasing interest in environmental issues, there has been a strong demand for fuel savings for automobiles, and rubber compositions used for automobile tires are also required to have excellent fuel economy. . As a rubber composition for automobile tires, a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer and a reinforcing agent is used.

  For example, as a polymer for improving fuel efficiency and a polymer composition having good fuel efficiency, Patent Document 1 discloses living butadiene, styrene and bis (diethylamino) methylvinylsilane using alkyllithium as a polymerization initiator. An anionically polymerized polymer and a polymer composition containing the polymer and silica have been proposed. Patent Document 2 proposes a polymer obtained by polymerizing butadiene and styrene by adding alkyllithium and hexamethyleneimine.

JP 2010-77386 A Japanese Patent Laid-Open No. 9-110942

  However, a polymer composition using the above-described conventional conjugated diene polymer has not been sufficiently satisfactory in terms of fuel economy.

  Under such circumstances, the problem to be solved by the present invention is a method for producing a conjugated diene polymer capable of obtaining a polymer composition having excellent fuel economy, and a conjugated diene polymer obtained by the production method. It is an object of the present invention to provide a polymer composition containing a coalescence and the conjugated diene polymer and a reinforcing agent.

（式中、Ｒ¹¹はケイ素原子、窒素原子及び酸素原子からなる原子群より選択される少なくとも一種の原子をヘテロ原子として有していてもよい炭素原子数３〜２０のヒドロカルビレン基を表す。） In the first aspect of the present invention, the following compounds (I) and (II) are added as compounds (I) and (II) as polymerization initiator components in a solution containing hydrocarbon as a solvent and containing at least one monomer component. ) In this order, and a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound is polymerized.
(I) Organic alkali metal compound (II) Compound represented by the following formula (1)

(In the formula, R ¹¹ represents a hydrocarbylene group having 3 to 20 carbon atoms which may have at least one atom selected from the group consisting of silicon atom, nitrogen atom and oxygen atom as a hetero atom. .)

  The second of the present invention relates to a conjugated diene polymer produced by the production method.

  3rd of this invention contains the said conjugated diene polymer and a reinforcing agent, and content of a reinforcing agent is 10 to 150 weight part per 100 weight part of conjugated diene polymers. It relates to a polymer composition.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the conjugated diene polymer which can obtain the polymer composition excellent in fuel-saving property, the conjugated diene polymer obtained by the said manufacturing method, and this conjugated diene polymer And a polymer composition containing a reinforcing agent can be provided.

  In the present specification, the hydrocarbyl group represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon. The hydrocarbylene group represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon. The hydrocarbyloxy group represents a monovalent group having a structure in which a hydrogen atom of a hydroxy group is replaced with a hydrocarbyl group. A substituted amino group is a group having a structure in which at least one hydrogen atom of an amino group is replaced by a monovalent atom other than a hydrogen atom or a monovalent group, or two hydrogen atoms of an amino group are divalent groups Represents a group having a structure replaced by The hydrocarbyl group having a substituent (hereinafter sometimes referred to as a substituted hydrocarbyl group) represents a monovalent group having a structure in which at least one hydrogen atom of the hydrocarbyl group is replaced with a substituent. A hydrocarbylene group having a heteroatom (hereinafter sometimes referred to as a heteroatom-containing hydrocarbylene group) is a carbon atom and / or hydrogen other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed. A divalent group having a structure in which an atom is replaced with a group having a hetero atom (an atom other than a carbon atom or a hydrogen atom) is represented.

（式中、Ｒ¹¹はケイ素原子、窒素原子及び酸素原子からなる原子群より選択される少なくとも一種の原子をヘテロ原子として有していてもよい炭素原子数３〜２０のヒドロカルビレン基を表す。） In the method for producing a conjugated diene polymer of the present invention, the following compounds (I) and (II) are compounded as compounds of polymerization initiator components in a solution containing hydrocarbon as a solvent and containing at least one monomer component ( A monomer component containing a conjugated diene compound and a silicon-containing vinyl compound is polymerized by adding I) and compound (II) in this order.
(I) Organic alkali metal compound (II) Compound represented by the following formula (1)

(In the formula, R ¹¹ represents a hydrocarbylene group having 3 to 20 carbon atoms which may have at least one atom selected from the group consisting of silicon atom, nitrogen atom and oxygen atom as a hetero atom. .)

  The solution using the hydrocarbon to which the compound (I) is added as a solvent contains at least one monomer component. Examples of the monomer component include conjugated diene compounds, silicon-containing vinyl compounds, and aromatic vinyl compounds.

  The solution using the hydrocarbon to which the compound (I) is added as a solvent is preferably a solution containing a conjugated diene compound.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and preferably 1,3-butadiene. Or isoprene.

（式中、ｍは０又は１であり、Ｒ²¹はヒドロカルビレン基を表し、Ｘ¹、Ｘ²及びＸ³は、置換アミノ基、ヒドロカルビルオキシ基、又は置換基を有していてもよいヒドロカルビル基を表す。） The silicon-containing vinyl compound is preferably a compound represented by the following formula (2).

(In the formula, m is 0 or 1, R ²¹ represents a hydrocarbylene group, and X ¹ , X ^2, and X ³ may have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents a hydrocarbyl group.)

  In the formula (2), m is 0 or 1, preferably 0.

Examples of the hydrocarbylene group for R ²¹ include an alkylene group, an alkenediyl group, an arylene group, and a group in which an arylene group and an alkylene group are bonded. Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Examples of the alkenediyl group include a vinylene group and an ethylene-1,1-diyl group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and a methylene group are bonded, and a group in which a phenylene group and an ethylene group are bonded.

R ²¹ is preferably an arylene group, more preferably a phenylene group.

In the formula (2), X ¹ , X ² and X ³ represent a substituted amino group, a hydrocarbyloxy group, or a hydrocarbyl group which may have a substituent. Preferably, at least one of X ¹ , X ² and X ³ is a substituted amino group, more preferably ^{two of} X ¹ , X ² and X ³ are substituted amino groups.

（Ｒ²²及びＲ²³は、置換基を有してもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表すか、あるいは、Ｒ²²とＲ²³とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表す。） The substituted amino group in X ¹ , X ² and X ³ is preferably a group represented by the following formula (2-A).

(R ²² and R ²³ represent a hydrocarbyl group or trihydrocarbyl silyl group which may have a substituent, or R ²² and R ²³ are bonded to each other to form a nitrogen atom and / or an oxygen atom. It represents a hydrocarbylene group that may be present as a hetero atom.)

The hydrocarbyl group which may have a substituent in R ²² and R ²³ is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group. Hydrocarbyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl. A chain alkyl group such as a group; a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group; and an aryl group such as a phenyl group, a benzyl group and a naphthyl group, an alkyl group is preferable, and a chain alkyl group is more preferable. A methyl group, an ethyl group, an n-propyl group, and an n-butyl group are more preferable. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, ethoxymethyl group, and methoxyethyl group; aryloxyalkyl groups such as a phenoxymethyl group.

The trihydrocarbyl silyl group in R ²² and R ^23, may be mentioned trimethylsilyl group, triethylsilyl group, a tri-alkyl silyl group such as tert- butyldimethylsilyl group.

The hydrocarbylene group optionally having a nitrogen atom and / or oxygen atom as a hetero atom in R ²² and R ²³ is a hetero atom-containing hydrocarbyl group or a hetero atom-containing hydrocarbyl group in which the hetero atom is a nitrogen atom and / or an oxygen atom. Carbylene group. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group. Examples of the hydrocarbylene group include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group, dodecamethylene group, 2,2,4-trimethylhexane-1,6. An alkylene group such as a diyl group; and an alkenediyl group such as a pentane-2-ene-1,5-diyl group. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom includes a group represented by -CH = N-CH = CH-
A group represented by —CH═N—CH ₂ —CH ₂ — can be exemplified. As the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom,
A group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — can be exemplified.

R ²² and R ²³ are preferably alkyl groups, or R ²² and R ²³ are preferably bonded to form an alkylene group, more preferably an alkyl group, and a methyl group or an ethyl group. Is more preferable.

Of the substituted amino groups represented by the formula (2-A), those in which R ²² and R ²³ are hydrocarbyl groups include dimethylamino group, diethylamino group, ethylmethylamino group, di-n-propylamino group, diisopropyl A dialkylamino group such as an amino group, a di-n-butylamino group, a diisobutylamino group, a di-sec-butylamino group, a di-tert-butylamino group; a diarylamino group such as a diphenylamino group; A dialkylamino group is preferable, and a dimethylamino group, a diethylamino group, a di-n-propylamino group, and a di-n-butylamino group are more preferable. Examples of the substituted hydrocarbyl group in which R ²² and R ²³ are bonded and the substituent is a hydrocarbyloxy group include di (alkoxyalkyl) amino such as di (methoxymethyl) amino group and di (ethoxymethyl) amino group You can raise a group. Examples of R ²² and R ²³ being trihydrocarbylsilyl groups include trialkylsilyl groups such as bis (trimethylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, and N-trimethylsilyl-N-methylamino group An amino group can be mentioned.

Among the substituted amino groups represented by the formula (2-A), those in which R ²² and R ²³ are bonded to form a hydrocarbylene group include a 1-trimethyleneimino group, a 1-pyrrolidinyl group, 1-alkylidino group such as 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino group, etc. it can. Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom include a 1-imidazolyl group and a 4,5-dihydro-1-imidazolyl group. Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is an oxygen atom include a morpholino group.

  The substituted amino group represented by the formula (2-A) is preferably a dialkylamino group or a 1-alkyleneimino group, more preferably a dialkylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, A di-n-butylamino group is more preferred.

Examples of the hydrocarbyloxy group in X ¹ , X ² and X ³ include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group; And aryloxy groups such as benzyloxy group.

The hydrocarbyl group which may have a substituent in X ¹ , X ² and X ³ is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group. Examples of the hydrocarbyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group; a phenyl group, a 4-methyl-1-phenyl group, An aryl group such as a benzyl group can be mentioned. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group. In these, an alkyl group is preferable and a C1-C10 alkyl group is more preferable.

Among the silicon-containing vinyl compounds represented by the formula (2), one of X ¹ , X ² and X ³ is a substituted amino group, and m is 0.
(Dimethylamino) dimethylvinylsilane, (ethylmethylamino) dimethylvinylsilane, (di-n-propylamino) dimethylvinylsilane, (diisopropylamino) dimethylvinylsilane, (dimethylamino) diethylvinylsilane, (ethylmethylamino) diethylvinylsilane, (di (Dialkylamino) dialkylvinylsilanes such as -n-propylamino) diethylvinylsilane, (diisopropylamino) diethylvinylsilane;
[Bis (trimethylsilyl) amino] dimethylvinylsilane, [bis (t-butyldimethylsilyl) amino] dimethylvinylsilane, [bis (trimethylsilyl) amino] diethylvinylsilane, [bis (t-butyldimethylsilyl) amino] diethylvinylsilane, etc. Bis (trialkylsilyl) amino] dialkylvinylsilane;
(Dimethylamino) di (methoxymethyl) vinylsilane, (dimethylamino) di (2-methoxyethyl) vinylsilane, (dimethylamino) di (ethoxymethyl) vinylsilane, (dimethylamino) di (2-ethoxyethyl) vinylsilane, (diethylamino (Dialkylamino) di (alkoxy) such as) di (methoxymethyl) vinylsilane, (diethylamino) di (2-methoxyethyl) vinylsilane, (diethylamino) di (ethoxymethyl) vinylsilane, (diethylamino) di (2-ethoxyethyl) vinylsilane Alkyl) vinylsilane;
Examples thereof include cyclic aminodialkylvinylsilane compounds such as 1-pyrrolidinyldimethylvinylsilane, 1-piperidinyldimethylvinylsilane, 1-hexamethyleneiminodimethylvinylsilane, 4,5-dihydro-1-imidazolyldimethylvinylsilane, morpholinodimethylvinylsilane, and the like. it can.

Among the silicon-containing vinyl compounds represented by the formula (2), one of X ¹ , X ² and X ³ is a substituted amino group, and m is 1,
(Dimethylamino) dimethyl-4-vinylphenylsilane, (dimethylamino) dimethyl-3-vinylphenylsilane, (diethylamino) dimethyl-4-vinylphenylsilane, (diethylamino) dimethyl-3-vinylphenylsilane, (di-n -Propylamino) dimethyl-4-vinylphenylsilane, (di-n-propylamino) dimethyl-3-vinylphenylsilane, (di-n-butylamino) dimethyl-4-vinylphenylsilane,
(Di-n-butylamino) dimethyl-3-vinylphenylsilane, (dimethylamino) diethyl-4-vinylphenylsilane, (dimethylamino) diethyl-3-vinylphenylsilane, (diethylamino) diethyl-4-vinylphenylsilane , (Diethylamino) diethyl-3-vinylphenylsilane, (di-n-propylamino) diethyl-4-vinylphenylsilane, (di-n-propylamino) diethyl-3-vinylphenylsilane,
(Dialkylamino) dialkylvinylphenylsilane such as (di-n-butylamino) diethyl-4-vinylphenylsilane and (di-n-butylamino) diethyl-3-vinylphenylsilane can be mentioned.

Of the silicon-containing vinyl compounds represented by formula (2), two of X ¹ , X ² and X ³ are substituted amino groups, and m is 0.
Bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (di-n-propylamino) methylvinylsilane, bis (di-n-butylamino) methylvinylsilane, bis (dimethylamino) ethylvinylsilane, bis (diethylamino) ) Bis (dialkylamino) alkylvinylsilanes such as ethylvinylsilane, bis (di-n-propylamino) ethylvinylsilane, bis (di-n-butylamino) ethylvinylsilane;
Bis [bis (trimethylsilyl) amino] methylvinylsilane, bis [bis (tert-butyldimethyl) amino] methylvinylsilane, bis [bis (trimethylsilyl) amino] ethylvinylsilane, bis [bis (tert-butyldimethyl) amino] ethylvinylsilane, etc. Of bis [bis (trialkylsilyl) amino] alkylvinylsilane;
Bis (dimethylamino) methoxymethylvinylsilane, bis (dimethylamino) (2-methoxyethyl) vinylsilane, bis (dimethylamino) ethoxymethylvinylsilane, bis (dimethylamino) (2-ethoxyethyl) vinylsilane, bis (diethylamino) methoxymethyl Bis (dialkylamino) alkoxyalkylvinylsilanes such as vinylsilane, bis (diethylamino) (2-methoxyethyl) vinylsilane, bis (diethylamino) ethoxymethylvinylsilane, bis (dimethylamino) (2-ethoxyethyl) vinylsilane;
Bis (1-pyrrolidinyl) methylvinylsilane, bis (1-piperidinyl) methylvinylsilane, bis (1-hexamethyleneimino) methylvinylsilane, bis (4,5-dihydro-1-imidazolyl) methylvinylsilane, bis (morpholino) methylvinylsilane And bis (cyclic amino) alkylvinylsilane compounds such as

Among the silicon-containing vinyl compounds represented by the formula (2), two of X ¹ , X ² and X ³ are substituted amino groups, and m is 1,
Bis (dimethylamino) methyl-4-vinylphenylsilane, bis (dimethylamino) methyl-3-vinylphenylsilane, bis (diethylamino) methyl-4-vinylphenylsilane, bis (diethylamino) methyl-3-vinylphenylsilane, Bis (di-n-propylamino) methyl-4-vinylphenylsilane, bis (di-n-propylamino) methyl-3-vinylphenylsilane, bis (di-n-butylamino) methyl-4-vinylphenylsilane Bis (di-n-butylamino) methyl-3-vinylphenylsilane, bis (dimethylamino) ethyl-4-vinylphenylsilane, bis (dimethylamino) ethyl-3-vinylphenylsilane, bis (diethylamino) ethyl- 4-vinylphenylsilane, bis (diethylamino) Til-3-vinylphenylsilane, bis (di-n-propylamino) ethyl-4-vinylphenylsilane, bis (di-n-propylamino) ethyl-3-vinylphenylsilane, bis (di-n-butylamino) And bis (dialkylamino) alkylvinylphenylsilane such as ethyl-4-vinylphenylsilane and bis (di-n-butylamino) ethyl-3-vinylphenylsilane.

Among the silicon-containing vinyl compounds represented by the formula (2), three of X ¹ , X ² and X ³ are substituted amino groups, and m is 0.
Examples thereof include tris (dialkylamino) vinylsilane such as tris (dimethylamino) vinylsilane, tris (diethylamino) vinylsilane, tris (di-n-propylamino) vinylsilane, and tris (di-n-butylamino) vinylsilane.

Of the silicon-containing vinyl compounds represented by the formula (2), three of X ¹ , X ² and X ³ are substituted amino groups, and m is 1,
Tris (dimethylamino) -4-vinylphenylsilane, tris (dimethylamino) -3-vinylphenylsilane, tris (diethylamino) -4-vinylphenylsilane,
Tris (diethylamino) -3-vinylphenylsilane, tris (di-n-propylamino) -4-vinylphenylsilane, tris (di-n-propylamino) -3-vinylphenylsilane, tris (di-n-butyl) And tris (dialkylamino) vinylphenylsilane such as amino) -4-vinylphenylsilane and tris (di-n-butylamino) -3-vinylphenylsilane.

Among the silicon-containing vinyl compounds represented by the formula (2), as compounds where X ¹ , X ² and X ³ are not substituted amino groups and m is 0,
Trialkoxyvinylsilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and tripropoxyvinylsilane; dialkoxyalkylvinylsilanes such as methyldimethoxyvinylsilane and methyldiethoxyvinylsilane; di (tert-pentoxy) phenylvinylsilane, di (tert-butoxy) phenylvinylsilane, and the like Dialkoxyaryl vinylsilanes; monoalkoxydialkylvinylsilanes such as dimethylmethoxyvinylsilane; monoalkoxydiarylvinylsilanes such as tert-butoxydiphenylvinylsilane, tert-pentoxydiphenylvinylsilane; tert-butoxymethylphenylvinylsilane, tert-butoxyethylphenylvinylsilane, etc. Monoalkoxyalkylarylvinylsila ; It can be mentioned tris (beta-methoxyethoxy) substituted alkoxy vinyl silane compounds such as vinyl silane.

  Further, examples of the silicon-containing vinyl compound include 4-N, N-bis (trimethylsilyl) aminostyrene, bis (trialkylsilyl) aminostyrene such as 3-N, N-bis (trimethylsilyl) aminostyrene; 4-bis (trimethylsilyl). ) Bis (trialkylsilyl) such as aminomethylstyrene, 3-bis (trimethylsilyl) aminomethylstyrene, 4- [2-bis (trimethylsilyl) aminoethyl] styrene, 3- [2-bis (trimethylsilyl) aminoethyl] styrene Aminoalkylstyrene can be mentioned.

The silicon-containing vinyl compound is preferably a compound represented by the formula (2), more preferably a compound in which m in the formula (2) is 0, and among X ¹ , X ² and X ^{3 in} the formula (2) A compound in which two are dialkylamino groups is more preferred, and a compound in which ^one of X ¹ , X ² and X ³ in formula (2) is an alkyl group is particularly preferred.

  Particularly preferred compounds as the silicon-containing vinyl compound are bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (di-n-propylamino) methylvinylsilane, and bis (di-n-butylamino) methylvinylsilane. .

In the monomer unit based on the compound represented by the formula (2), the groups represented by X ¹ , X ² and X ³ may be a hydroxyl group by hydrolysis or the like.

  In the present invention, the amount of the silicon-containing vinyl compound used is preferably 0.01% by weight or more, in order to improve fuel economy, with the total amount of monomer components used in the polymerization being 100% by weight. More preferably, it is 0.02 weight% or more, More preferably, it is 0.05 weight% or more. In order to increase economy and to increase the tensile strength at break, the content is preferably 20% by weight or less, more preferably 2% by weight or less, and further preferably 1% by weight or less.

  In the present invention, it is preferable to polymerize an aromatic vinyl compound as a monomer component in addition to the conjugated diene compound and the silicon-containing vinyl compound in order to increase the tensile strength at break. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like, and styrene is preferable.

  The amount of the aromatic vinyl compound used is 0% by weight or more (the amount of the conjugated diene compound used is 100% by weight or less), where the total amount of the conjugated diene compound and the aromatic vinyl compound is 100% by weight, preferably 10%. It is at least% by weight (the amount of conjugated diene compound used is 90% by weight or less), more preferably at least 15% by weight (the content of the conjugated diene compound is 85% by weight or less). In order to improve fuel economy, the content of the aromatic vinyl compound is preferably 50% by weight or less (the content of the conjugated diene compound is 50% by weight or more), more preferably 45% by weight or less (conjugated). The diene compound content is 55% by weight or more).

  Compound (I) is an organic alkali metal compound. Examples of organic alkali metal compounds include organic lithium compounds, organic sodium compounds, organic potassium compounds, and organic cesium compounds. Examples of the organic lithium compound include alkyl lithium such as methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, and n-octyl lithium. Lithium compounds; alkenyl lithium compounds such as vinyl lithium and propenyl lithium; aryl lithium compounds such as phenyl lithium, benzyl lithium, tolyl lithium and lithium naphthylide; tetramethylene dilithium, pentamethylene dilithium, hexamethylene dilithium, decamethylene di And alkylene dilithium compounds such as lithium; and lithium naphthalenide and lithium biphenylide. Examples of the organic sodium compound include sodium naphthalenide and sodium biphenylide. An example of the organic potassium compound is potassium naphthalenide. Compound (I) is preferably an organolithium compound, more preferably an alkyllithium compound having 1 to 20 carbon atoms, still more preferably n-butyllithium, sec-butyllithium, or tert-butyllithium. .

（式中、Ｒ¹¹はケイ素原子、窒素原子及び酸素原子からなる原子群より選択される少なくとも一種の原子をヘテロ原子として有していてもよい炭素原子数３〜２０のヒドロカルビレン基を表す。） Compound (II) is a compound represented by the following formula (1).

(In the formula, R ¹¹ represents a hydrocarbylene group having 3 to 20 carbon atoms which may have at least one atom selected from the group consisting of silicon atom, nitrogen atom and oxygen atom as a hetero atom. .)

In formula (1), the hydrocarbylene group having 3 to 20 carbon atoms which may have at least one atom selected from the group consisting of silicon atom, nitrogen atom and oxygen atom as a hetero atom is carbon. A hydrocarbylene group having 3 to 20 atoms or a heteroatom-containing hydrocarbylene having 3 to 20 carbon atoms, wherein the heteroatom is at least one atom selected from the group consisting of silicon atoms, nitrogen atoms and oxygen atoms It is a group. The heteroatom-containing hydrocarbylene group having 3 to 20 carbon atoms, wherein the heteroatom is at least one atom selected from the group consisting of silicon atom, nitrogen atom and oxygen atom, includes carbon whose heteroatom is a silicon atom A C3-C20 heteroatom-containing hydrocarbylene group, a C3-C20 heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, a C3-C20 carbon atom in which the heteroatom is an oxygen atom A hetero atom containing hydrocarbylene group can be mentioned. Examples of the hydrocarbylene group having 3 to 20 carbon atoms include tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, hexane-1,5-diyl group, and 2-methylpentane. -1,5-diyl group, 3-methylpentane-1,5-diyl group, 2,4-methylpentane-1,5-diyl group, 2,2,4-trimethylhexane-1,6-diyl group Examples of the heteroatom-containing hydrocarbylene group having 3 to 20 carbon atoms in which the hetero atom is a silicon atom include —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —Si ( CH _{3) 2} - group represented by may be mentioned. Examples of the heteroatom-containing hydrocarbylene group having 3 to 20 carbon atoms in which the heteroatom is a nitrogen atom include a group represented by —CH═N—CH═CH—, —CH═N—CH ₂ —CH ₂ — The group represented by can be mentioned. Examples of the heteroatom-containing hydrocarbylene group having 3 to 20 carbon atoms is a heteroatom is an oxygen _{atom, -CH 2 -CH 2 -O-CH} 2 -CH 2 - may be mentioned a group represented by.

R ¹¹ is preferably a hydrocarbylene group having 3 to 20 carbon atoms, more preferably an alkylene group having 4 to 8 carbon atoms, still more preferably a tetramethylene group, a pentamethylene group, or a hexamethylene group. is there.

When R ¹¹ is a hydrocarbylene group having 4 carbon atoms, the polymer composition is more excellent in tensile strength at break. The hydrocarbylene group having 4 carbon atoms is preferably an alkylene group having 4 carbon atoms. The compound represented by the formula (1) in which R ¹¹ is the alkylene group is pyrrolidine.

When R ¹¹ is a hydrocarbylene group having 5 to 8 carbon atoms, the polymer composition is more excellent in gripping properties. The hydrocarbylene group having 5 to 8 carbon atoms is preferably an alkylene group having 5 to 8 carbon atoms. The compound represented by the formula (1) in which R ¹¹ is the alkylene group is preferably piperidine or hexamethyleneimine.

Among the compounds represented by the formula (1), compounds wherein R ¹¹ is a hydrocarbylene group having 3 to 20 carbon atoms include trimethyleneimine, pyrrolidine, piperidine, 2-methylpiperidine, hexamethyleneimine, octane Methyleneimine, decamethyleneimine, dodecamethyleneimine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 1,2,3,6-tetrahydropyridine, 3,5,5- Examples thereof include trimethylhexahydroazepine and 1,3,3-trimethyl-6-azabicyclo [3,2,2] octane.

Among the compounds represented by the formula (1), the compound in which R ¹¹ is a heteroatom-containing hydrocarbylene group having 3 to 20 carbon atoms includes 2, 2, 5, 5-tetramethyl-1-aza-2,5-disilacyclopentane;
Examples of the hetero atom as a nitrogen atom include imidazole and 4,5-dihydroimidazole; and examples of the hetero atom as an oxygen atom include morpholine.

  Particularly preferred as the compound represented by the formula (1) are pyrrolidine, piperidine, and hexamethyleneimine.

  In the present invention, compounds (I) and (II) are added as a polymerization initiator component in the order of compound (I) and compound (II) in a solution containing hydrocarbon as a solvent and containing at least one monomer component. In addition, the monomer component containing the conjugated diene compound and the silicon-containing vinyl compound is polymerized. Preferably, after adding the compound (I) to the solution, the compound (II) is added to the solution while the polymerization conversion rate of the monomer component is 5% by weight or less. The polymerization conversion rate is a value in which the amount of monomer components used in the polymerization in this production method is 100% by weight.

  Examples of the monomer component contained in the solution using the hydrocarbon to which the compound (I) is added as a solvent include conjugated diene compounds, silicon-containing vinyl compounds, aromatic vinyl compounds, and the like, preferably conjugated diene compounds. It is.

  The concentration of the monomer component in the solution using the hydrocarbon as a solvent is preferably 1% by weight to 50% by weight, and more preferably 5% by weight to 30% by weight.

  It is preferable that the addition amount of the compound (I) in this manufacturing method is 0.01 mmol-15 mmol per 100g of monomer components used by superposition | polymerization.

  In this production method, the amount of the compound (II) added while the polymerization conversion rate of the monomer component is 5% by weight or less is preferably 0.5 mol to 2 with respect to 1 mol of the compound (I) added. 0.0 mol, more preferably 0.8 mol to 1.5 mol.

  Even after the polymerization conversion rate of the monomer component exceeds 5% by weight, the compound (II) may be added. The addition amount of the compound (II) after the polymerization conversion rate of the monomer component exceeds 5% by weight is preferably 0.5 mol or less with respect to 1 mol of the addition amount of the compound (I).

  Further, after adding the compound (II) to a solution using a hydrocarbon as a solvent, a monomer component may be further added to the solution.

  The hydrocarbon used for the preparation of the solution using a hydrocarbon as a solvent is a compound that does not deactivate the compound (I), and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and n-octane. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. The hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.

  Polymerization reaction is an agent that adjusts the amount of vinyl bonds of conjugated diene units, an agent that adjusts the distribution of monomer units based on monomers other than conjugated diene units and conjugated dienes in the conjugated diene polymer chain , And collectively referred to as “regulators”). Examples of such agents include ether compounds, tertiary amine compounds, and phosphine compounds. Examples of the ether compound include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethylene glycol diethyl ether. And aliphatic ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine compound include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. One or more of these are used.

  The polymerization temperature in the present invention is usually 25 ° C to 100 ° C, preferably 35 ° C to 90 ° C. More preferably, it is 50 degreeC-80 degreeC. The polymerization time is usually 10 minutes to 5 hours.

  In the method for producing a conjugated diene polymer of the present invention, a compound containing a nitrogen atom and / or a silicon atom may be reacted with an active terminal of a polymer produced by polymerization.

  Among the compounds containing a nitrogen atom and / or a silicon atom, preferred are compounds containing a nitrogen atom and a carbonyl group.

（式（３）中、Ｒ³¹とＲ³²とは結合していてもよいか、あるいは、Ｒ³¹とＲ³⁴とは結合してしてもよく、Ｒ³¹は置換基を有してもよいヒドロカルビル基、Ｒ³²と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、あるいは、Ｒ³⁴と結合して２価基を表し、Ｒ³²は置換基を有してもよいヒドロカルビル基、あるいは、Ｒ³¹と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³⁴は置換基を有してもよいヒドロカルビル基、水素原子、あるいは、Ｒ³¹と結合して２価基を表す。また、Ｒ³³は２価基を表し、ｋは０又は１を表す。） As the compound containing a nitrogen atom and a carbonyl group, a compound represented by the following formula (3) is preferable.

(In Formula (3), R ³¹ and R ³² may be bonded, or R ³¹ and R ³⁴ may be bonded, and R ³¹ may have a substituent. A hydrocarbyl group, a hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom as a hetero atom bonded to R ³² , or a divalent group bonded to R ³⁴ , wherein R ³² represents a substituent Or a hydrocarbylene group which may be bonded to R ³¹ and optionally have a nitrogen atom and / or an oxygen atom as a hetero atom, and R ³⁴ has a substituent. And may be a hydrocarbyl group, a hydrogen atom, or a divalent group bonded to R ^31. R ³³ represents a divalent group, and k represents 0 or 1.)

In the formula (3), the hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group, and a substituted hydrocarbyl group in which the substituent is a substituted amino group. Examples of the hydrocarbyl group include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group; alkenyl groups such as vinyl group, allyl group and isopropenyl group; and aryl groups such as phenyl group. be able to. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group. Examples of the substituted hydrocarbyl group in which the substituent is a substituted amino group include 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, and 3- (N, N-dimethylamino) propyl. Group, (N, N-dialkylamino) alkyl group such as 3- (N, N-diethylamino) propyl group; 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl Groups, (N, N-dialkylamino) aryl groups such as 4- (N, N-diethylamino) phenyl group, 3- (N, N-diethylamino) phenyl group; 4- (N, N-dimethylamino) methylphenyl Groups, (N, N-dialkylamino) alkylaryl groups such as 4- [2- (N, N-dimethylamino) ethyl] phenyl group; 3- (1-pyrrolidinyl) propyl group Cyclic amino group-containing alkyl groups such as 3- (1-piperidinyl) propyl group and 3- (1-imidazolyl) propyl group; 4- (1-pyrrolidinyl) phenyl group, 4- (1-piperidinyl) phenyl group, 4- Cyclic amino group-containing aryl groups such as (1-imidazolyl) phenyl group; 4- [2- (1-pyrrolidinyl) ethyl] phenyl group, 4- [2- (1-piperidinyl) ethyl] phenyl group, 4- [2 And a cyclic amino group-containing alkylaryl group such as-(1-imidazolyl) ethyl] phenyl group.

In the formula (3), the hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom to which R ³¹ and R ³² are bonded as a hetero atom is a hydrocarbylene group or a hetero atom having a nitrogen atom and And / or a heteroatom-containing hydrocarbylene group which is an oxygen atom. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group. Examples of the hydrocarbylene group include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, alkylene group such as 2,2,4-trimethylhexane-1,6-diyl group; 1,4-phenylene group, etc. Of the arylene group. As the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom,
A group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ — can be exemplified. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom include groups represented by — (CH ₂ ) _s —O— (CH ₂ ) _t — (s and t are integers of 1 or more). Can do.

In the formula (3), the divalent group in which R ³¹ and R ³⁴ are bonded and the divalent group of R ³³ include a hydrocarbylene group, a heteroatom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom, hetero A heteroatom-containing hydrocarbylene group in which the atom is an oxygen atom, a group in which a hydrocarbylene group and an oxygen atom are bonded, a hydrocarbylene group and a group represented by —NR ³⁵ — (R ³⁵ is a hydrocarbyl group or a hydrogen atom And a group bonded to each other. Examples of the hydrocarbylene group include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, alkylene group such as 2,2,4-trimethylhexane-1,6-diyl group; 1,4-phenylene group, etc. Of the arylene group. As the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom,
A group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ — can be exemplified. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom include groups represented by — (CH ₂ ) _s —O— (CH ₂ ) _t — (s and t are integers of 1 or more). Can do. As a group in which a hydrocarbylene group and an oxygen atom are bonded,
A group represented by — (CH ₂ ) _r —O— (r represents an integer of 1 or more) can be exemplified. As a group in which a hydrocarbylene group and a group represented by —NR ³⁵ — (R ³⁵ represents a hydrocarbyl group or a hydrogen atom) are bonded, a group represented by — (CH ₂ ) _p —NR ³⁵ — ( R ³⁵ represents a hydrocarbyl group having 1 to 6 carbon atoms, or a hydrogen atom, and p represents an integer of 1 or more.

（式（３−Ａ）中、Ｒ³¹とＲ³²とが結合していてもよく、Ｒ³¹は置換基を有してもよいヒドロカルビル基を表すか、Ｒ³²と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³²は置換基を有してもよいヒドロカルビル基を表すか、Ｒ³¹と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³⁴は置換基を有してもよいヒドロカルビル基又は水素原子を表す。） Preferred examples of the compound represented by the formula (3) include a compound represented by (3-A) in which k is 0 and R ³⁴ is a hydrocarbyl group or a hydrogen atom which may have a substituent. it can.

(In Formula (3-A), R ³¹ and R ³² may be bonded to each other, and R ³¹ represents a hydrocarbyl group which may have a substituent, or bonded to R ³² and bonded to a nitrogen atom and / Alternatively, it represents a hydrocarbylene group which may have an oxygen atom as a hetero atom, and R ³² represents a hydrocarbyl group which may have a substituent, or is bonded to R ³¹ to form a nitrogen atom and / or an oxygen atom. Represents a hydrocarbylene group optionally having a hetero atom, and R ³⁴ represents a hydrocarbyl group or a hydrogen atom optionally having a substituent.

In the formula (3-A), a hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ , a nitrogen atom and / or an oxygen atom bonded to R ³¹ and R ³² as a hetero atom The description and examples of the hydrocarbylene group which may be present are the same as those described in the description of the formula (3).

In the formula (3-A), R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms or a hetero atom bonded to R ³² or a hetero atom is a nitrogen atom. It is a C3-C10 hetero atom containing hydrocarbylene group which is. More preferably, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or an alkylene group having 3 to 10 carbon atoms bonded to R ³² , —CH═N—CH═ It is a group represented by CH— or a group represented by —CH═N—CH ₂ —CH ₂ —. More preferably, it is a C1-C6 alkyl group. Particularly preferred is a methyl group or an ethyl group.

In the formula (3-A), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbon group having 3 to 10 carbon atoms bonded to R ³¹ or a hetero atom is a nitrogen atom. It is a C3-C10 hetero atom containing hydrocarbylene group which is. More preferably, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or an alkylene group having 3 to 10 carbon atoms bonded to R ³¹ , —CH═N—CH═. It is a group represented by CH— or a group represented by —CH═N—CH ₂ —CH ₂ —. More preferably, it is a C1-C6 alkyl group. Particularly preferred is a methyl group or an ethyl group.

In the formula (3-A), R ³⁴ is preferably a hydrocarbyl group or a hydrogen atom, more preferably a hydrocarbyl group or a hydrogen atom having 1 to 10 carbon atoms, and still more preferably an alkyl having 1 to 6 carbon atoms. Group or hydrogen atom, particularly preferably a hydrogen atom, a methyl group or an ethyl group.

Among the compounds represented by the formula (3-A), those in which R ³⁴ is a hydrocarbyl group include N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-ethylacetamide and the like. N, N-dihydrocarbylacetamide; N, N-dihydrocarbylacrylamide such as N-dimethylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide; N, N-dimethylmethacrylamide, N, N-diethyl Examples thereof include N, N-dihydrocarbyl methacrylamide such as methacrylamide and N-methyl-N-ethyl methacrylamide.

Among the compounds represented by the formula (3-A), those in which R ³⁴ is a hydrogen atom include N, N-dimethylformamide, N, N-dimethylformamide, N-methyl-N-ethylformamide and the like. , N-dihydrocarbylformamide.

（式（３−Ｂ）中、Ｒ³²は置換基を有してもよいヒドロカルビル基を表し、Ｒ³⁶はヒドロカルビレン基と−ＮＲ³⁵−で表される基とが結合した基又はヒドロカルビレン基を表し、Ｒ³⁵はヒドロカルビル基又は水素原子を表す。Ｒ³⁵が結合した窒素原子は、Ｃ＝Ｏの炭素原子と結合する。） Preferred examples of the compound represented by the formula (3) include a compound represented by (3-B) in which k is 0 and R ³⁴ is bonded to R ³¹ to form a divalent group.

(In the formula (3-B), R ³² represents a hydrocarbyl group which may have a substituent, and R ³⁶ represents a group in which a hydrocarbylene group and a group represented by —NR ³⁵ — are bonded or a hydrocarbyl group. R ³⁵ represents a hydrocarbyl group or a hydrogen atom, and the nitrogen atom to which R ³⁵ is bonded is bonded to a carbon atom of C═O.)

In the formula (3-B), the description and illustration of the hydrocarbyl group which may have a substituent of R ³² are the same as those described in the description of the formula (3).

In the formula (3-B), examples of the hydrocarbylene group of R ³⁶ include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexane-1,6-diyl group, and the like. An arylene group such as a 1,4-phenylene group. The group of R ³⁶ in which the hydrocarbylene group and the group represented by —NR ³⁵ — (R ³⁵ represents a hydrocarbyl group or a hydrogen atom) is bonded to — (CH ₂ ) _p —NR ³⁵ —. And a group represented by the formula (R ³⁵ represents a hydrocarbyl group or a hydrogen atom, and p represents an integer of 1 or more).

In the formula (3-B), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, More preferred are alkyl groups having 1 to 6 carbon atoms or phenyl groups, and particularly preferred are methyl group, ethyl group and phenyl group.

In the formula (3-B), R ³⁶ is preferably a hydrocarbylene group having 1 to 10 carbon atoms, or a group represented by —NR ³⁵ — and a hydrocarbylene group having 1 to 10 carbon atoms (R ³⁵ represents a hydrocarbyl group having 1 to 10 carbon atoms or a hydrogen atom.), More preferably an alkylene group having 3 to 6 carbon atoms or — (CH ₂ ) _p —NR ³⁵ —. Represented by the group (R ³⁵ represents a hydrocarbyl group having 1 to 10 carbon atoms, and p represents an integer of 2 to 5), more preferably a trimethylene group, a tetramethylene group, a pentamethylene group, or — It is a group represented by (CH ₂ ) ₂ —N (CH ₃ ) —.

Among the compounds represented by the formula (3-B), those in which R ³⁶ is a hydrocarbylene group include N-methyl-β-propiolactam, N-phenyl-β-propiolactam and the like N- Hydrocarbyl-β-propiolactam; N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-methyl-5-methyl- N-hydrocarbyl-2-pyrrolidone such as 2-pyrrolidone; N-hydrocarbyl-2-piperidone such as N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2-piperidone; N-methyl- N-hydrocarbyl-ε-caprolactam such as ε-caprolactam, N-phenyl-ε-caprolactam; N-methyl-ω-laurolactam, - it can be mentioned N- hydrocarbyl -ω- Lau Lilo lactams such as vinyl -ω- Lau Lilo lactam. R ³⁶ is preferably an alkylene group having 3 to 6 carbon atoms, and R ³² is an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably R ³⁶ is a trimethylene group or a tetramethylene group. , A pentamethylene group, and a compound wherein R ³² is a methyl group, an ethyl group or a phenyl group, more preferably N-phenyl-2-pyrrolidone or N-methyl-ε-caprolactam.

Of the compounds represented by the formula (3-B), R ³⁶ is a group in which a hydrocarbylene group and a group represented by —NR ³⁵ — (R ³⁵ is a hydrocarbyl group or a hydrogen atom) are combined. 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-divinyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone Mention may be made of 1,3-dihydrocarbyl-2-imidazolidinone such as non. Preferably, R ³⁶ is a group represented by — (CH ₂ ) _p —NR ³⁵ — (R ³⁵ represents a hydrocarbyl group having 1 to 10 carbon atoms, and p represents an integer of 2 to 5). , R ³² is a compound having 1 to 6 carbon atoms or a phenyl group, more preferably, R ³⁶ is a group represented by — (CH ₂ ) ₂ —N (CH ₃ ) —, A compound in which R ³² is a methyl group or an ethyl group, and more preferably 1,3-dimethyl-2-imidazolidinone.

（式（３−Ｃ）中、Ｒ³¹とＲ³²が結合していてもよく、Ｒ³¹は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ³²と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³²は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ³¹と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³³はヒドロカルビレン基を表し、Ｒ³⁴は置換基を有してもよいヒドロカルビル基を表す。） Preferable compounds represented by the formula (3) include compounds represented by the following formula (3-C) in which k is 1 and R ³³ is a hydrocarbylene group.

(In the formula (3-C), R ³¹ and R ³² may be bonded, and R ³¹ represents a hydrocarbyl group which may have a substituent, or bonded to R ³² to form a nitrogen atom and / or Alternatively, it represents a hydrocarbylene group that may have an oxygen atom as a hetero atom, and R ³² represents a hydrocarbyl group that may have a substituent, or is bonded to R ³¹ to form a nitrogen atom and / or oxygen. (It represents a hydrocarbylene group that may have an atom as a hetero atom, R ³³ represents a hydrocarbylene group, and R ³⁴ represents a hydrocarbyl group that may have a substituent.)

In the formula (3-C), the hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ , a nitrogen atom and / or an oxygen atom bonded to R ³¹ and R ³² as a hetero atom The description and examples of the hydrocarbylene group which may be optionally substituted and the hydrocarbylene group of R ³³ are the same as those described in the description of the formula (3).

In the formula (3-C), R ³³ is preferably a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. More preferably an alkylene group having 1 to 6 carbon atoms or a phenylene group, and particularly preferably an ethylene group, a trimethylene group or a 1,4-phenylene group.

In the formula (3-C), R ³⁴ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 3 to 10 carbon atoms in which the substituent is a dialkylamino group, more preferably a carbon atom. An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a dialkylaminoalkyl group having 3 to 6 carbon atoms, or a dialkylaminoaryl group having 8 to 10 carbon atoms, more preferably a methyl group, An ethyl group, a dialkylaminomethyl group having 3 to 6 carbon atoms, a dialkylaminoethyl group having 4 to 6 carbon atoms, a phenyl group, and a dialkylaminophenyl group having 8 to 10 carbon atoms.

In the formula (3-C), R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³² , or a hetero atom being a nitrogen atom Or a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
An alkylene group having 3 to 10 carbon atoms bonded to R ³² , a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — ( CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or a group having 3 to 6 carbon atoms bonded to R ³² . An alkylene group, a group represented by -CH = N-CH = CH-,
A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a tetramethylene group, a hexamethylene group, —CH═N— bonded to R ^32. It is a group represented by CH = CH-.

In the formula (3-C), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³¹ , or a hetero atom being a nitrogen atom Or a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
An alkylene group having 3 to 10 carbon atoms bonded to R ³¹ , a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — ( CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or a group having 3 to 6 carbon atoms bonded to R ³¹ . An alkylene group, a group represented by -CH = N-CH = CH-,
A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a tetramethylene group, a hexamethylene group, —CH═N— bonded to R ^31. It is a group represented by CH = CH-.

Among the compounds represented by the formula (3-C), compounds in which R ³³ is an arylene group and R ³⁴ is an alkyl group include 4- (N, N-dimethylamino) acetophenone, 4- (N— 4- (N, N-dihydrocarbylamino) acetophenone such as methyl-N-ethylamino) acetophenone, 4- (N, N-diethylamino) acetophenone; 4-cyclic such as 4 ′-(imidazol-1-yl) acetophenone Examples thereof include aminoacetophenone compounds. Among these, 4-cyclic aminoacetophenone compounds are preferable, and 4 ′-(imidazol-1-yl) acetophenone is more preferable.

Among the compounds represented by the formula (3-C), as a compound in which R ³³ is an arylene group and R ³⁴ is an aryl group or a substituted aryl group, 1,7-bis (methylethylamino) -4- Bis (dihydrocarbylaminoalkyl) ketones such as heptanone, 1,3-bis (diphenylamino) -2-propanone; 4-N, N-dimethylaminobenzophenone, 4-N, N-diethylaminobenzophenone, 4-N, N 4- (dihydrocarbylamino) benzophenone such as di-t-butylaminobenzophenone, 4-N, N-diphenylaminobenzophenone; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) 4,4′-bis (dihydride) such as benzophenone and 4,4′-bis (diphenylamino) benzophenone Karubiruamino) benzophenone can be mentioned. Among these, R ³¹ and R ³² are alkyl groups having 1 to 6 carbon atoms, R ³³ is a phenylene group, and R ³⁴ is a phenyl group or a dialkylaminophenyl group having 8 to 10 carbon atoms. Compounds are preferred, and 4-N, N-dimethylaminobenzophenone, 4-N, N-diethylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone are more preferred.

（式（３−Ｄ）中、Ｒ³¹とＲ³²が結合していてもよく、Ｒ³¹は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ³²と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³²は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ³¹と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ³⁷はヒドロカルビレン基を表し、Ａは酸素原子又は−ＮＲ³⁵−を表し、Ｒ³⁵はヒドロカルビレン基又は水素原子を表し、Ｒ³⁴は置換基を有してもよいヒドロカルビル基を表す。） As a preferred compound represented by the formula (3), k is 1, and R ³³ is a group in which a hydrocarbylene group and an oxygen atom are bonded, or a group represented by a hydrocarbylene group and —NR ³⁵ — ( R ³⁵ represents a compound represented by the following formula (3-D) which is a group bonded to a hydrocarbyl group or a hydrogen atom.

(In Formula (3-D), R ³¹ and R ³² may be bonded to each other, and R ³¹ represents a hydrocarbyl group which may have a substituent, or bonded to R ³² and bonded to a nitrogen atom and / Alternatively, it represents a hydrocarbylene group that may have an oxygen atom as a hetero atom, and R ³² represents a hydrocarbyl group that may have a substituent, or is bonded to R ³¹ to form a nitrogen atom and / or oxygen. Represents a hydrocarbylene group which may have an atom as a hetero atom, R ³⁷ represents a hydrocarbylene group, A represents an oxygen atom or —NR ³⁵ —, and R ³⁵ represents a hydrocarbylene group or a hydrogen atom. R ³⁴ represents a hydrocarbyl group which may have a substituent.

In the formula (3-D), a hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ , a nitrogen atom and / or an oxygen atom in which R ³¹ and R ³² are bonded as a hetero atom The description and examples of the hydrocarbylene group which may be present are the same as those described in the description of the formula (3).

In Formula (3-D), A is preferably an oxygen atom or a group represented by —NR ³⁵ — (R ³⁵ is a hydrocarbylene group having 1 to 5 carbon atoms or a hydrogen atom), and more A group represented by an oxygen atom or -NH- is preferred, and a group represented by -NH- is more preferred.

In formula (3-D), examples of the hydrocarbylene group for R ³⁷ include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexane-1,6-diyl group, and the like. An arylene group such as a 1,4-phenylene group.

In the formula (3-D), R ³⁴ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, still more preferably a vinyl group or an isopropenyl group. And particularly preferably a vinyl group.

In the formula (3-D), R ³⁷ is preferably a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an ethylene group or a trimethylene group. And particularly preferably a trimethylene group.

In the formula (3-D), R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³² , or a hetero atom is a nitrogen atom Or a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
An alkylene group having 3 to 10 carbon atoms bonded to R ³² , a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — ( CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or a group having 3 to 6 carbon atoms bonded to R ³² . An alkylene group, a group represented by -CH = N-CH = CH-,
A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a tetramethylene group, a hexamethylene group, —CH═N— bonded to R ^32. It is a group represented by CH = CH-.

In the formula (3-D), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³¹ , or a hetero atom is a nitrogen atom. Or a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
An alkylene group having 3 to 10 carbon atoms bonded to R ³¹ , a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — ( CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or a group having 3 to 6 carbon atoms bonded to R ³¹ . An alkylene group, a group represented by -CH = N-CH = CH-,
A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a tetramethylene group, a hexamethylene group, —CH═N— bonded to R ^31. It is a group represented by CH = CH-.

Among the compounds represented by formula (3-D), as the compound in which A is an oxygen atom,
2- (Dihydrocarbylamino) ethyl acrylate such as 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate; 3- (Dihydrocarbylamino) propyl acrylate such as 3- (dimethylamino) propyl acrylate; Examples thereof include 2- (dihydrocarbylamino) ethyl methacrylate such as (dimethylamino) ethyl methacrylate and 2- (diethylamino) ethyl methacrylate; and 3- (dihydrocarbylamino) propyl methacrylate such as 3- (dimethylamino) propyl methacrylate. . As the compound in which A is an oxygen atom, R ³¹ and R ³² are alkyl groups having 1 to 6 carbon atoms, R ³⁴ is a vinyl group or an isopropenyl group, and R ³⁷ is an ethylene group or a trimethylene group. A compound is preferable, and a compound in which R ³¹ and R ³² are a methyl group or an ethyl group, R ³⁴ is a vinyl group, and R ³⁷ is a trimethylene group is more preferable.

Among the compounds represented by the formula (3-D), as a compound in which A is a group represented by —NR ³⁵ — (R ³⁵ is a hydrocarbylene group or a hydrogen atom),
N- (2-dihydrocarbylaminoethyl) acrylamide such as N- (2-dimethylaminoethyl) acrylamide, N- (2-diethylaminoethyl) acrylamide; N- (3-dimethylaminopropyl) acrylamide, N- (3- N- (3-dihydrocarbylaminopropyl) acrylamide such as diethylaminopropyl) acrylamide; N- (4-dihydrocarbylaminobutyl) such as N- (4-dimethylaminobutyl) acrylamide, N- (4-diethylaminobutyl) acrylamide N- (2-dihydrocarbylaminoethyl) methacrylamide such as acrylamide; N- (2-dimethylaminoethyl) methacrylamide, N- (2-diethylaminoethyl) methacrylamide; N- (3-dimethylaminopropylene ) N- (3-dihydrocarbylaminopropyl) methacrylamide such as methacrylamide, N- (3-diethylaminopropyl) methacrylamide; N- (4-dimethylaminobutyl) methacrylamide, N- (4-diethylaminobutyl) methacryl Mention may be made of N- (4-dihydrocarbylaminobutyl) methacrylamide such as amide. Among these, A is a group represented by —NH—, R ³¹ and R ³² are alkyl groups having 1 to 6 carbon atoms, R ³⁴ is a vinyl group or an isopropenyl group, and R ³⁷ In which R is an ethylene group or a trimethylene group, A is a group represented by —NH—, R ³¹ and R ³² are a methyl group or an ethyl group, R ³⁴ is a vinyl group, and R ³⁷ is More preferred are compounds that are trimethylene groups.

  In addition to the above, examples of the compound containing a nitrogen atom and / or a silicon atom include a compound containing an alkoxysilyl group.

As a compound containing an alkoxysilyl group,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane; trialkoxyhydrocarbylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane; trimethoxychlorosilane, Trialkoxyhalosilanes such as triethoxychlorosilane and tri-n-propoxychlorosilane; dialkoxydihydrocarbylsilanes such as dimethoxydimethylsilane, diethoxydimethylsilane and dimethoxydiethylsilane; dimethoxydichlorosilane, diethoxydichlorosilane and di-n- Dialkoxydihalosilanes such as propoxydichlorosilane; monoalkoxytrihydrocarbylsilanes such as methoxytrimethylsilane Monoalkoxytrihalosilanes such as methoxytrichlorosilane and ethoxytrichlorosilane; 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycid (Glycidoxyalkyl) alkylalkoxysilane compounds such as xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane; 2- (3,4-epoxycyclohexyl) (3,4-epoxycyclohexyl) alkylalkoxysilane compounds such as ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; [2- (3,4-epoxycyclohexyl) ethyl [(3,4-epoxycyclohexyl) alkyl] alkylalkoxysilane compounds such as methyldimethoxysilane; alkoxysilylalkylsuccinic anhydrides such as 3-trimethoxysilylpropyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride Products; (methacryloyloxyalkyl) alkoxysilane compounds such as 3-methacryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane; [3- (dimethylamino) propyl] trimethoxysilane, [3- ( Diethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] methyldiethoxysilane, [2- (dimethylamino) ethyl] triethoxysilane Lan, [(dialkylamino) alkyl] alkoxysilane compounds such as [2- (dimethylamino) ethyl] trimethoxysilane; (1-hexamethyleneiminomethyl) trimethoxysilane, [3- (1-hexamethyleneimino) propyl ] Cyclic aminoalkylalkoxysilanes such as triethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole {{[Di (tetrahydrofuranyl) amino] alkyl} alkoxysilanes such as {3- [di (tetrahydrofuranyl) amino] propyl} trimethoxysilane, {3- [di (tetrahydrofuranyl) amino] propyl} triethoxysilane, etc. Compound; {3- [N, N-bis (trimethylsilyl) [N, N-bis (trialkylsilyl) aminoalkyl] alkylalkoxysilane compounds such as amino] propyl} methyldimethoxysilane and {3- [N, N-bis (trimethylsilyl) amino] propyl} methyldiethoxysilane be able to. As the [(dialkylamino) alkyl] alkoxysilane compound, the alkyl group of the dialkylamino group is an alkyl group having 1 to 4 carbon atoms, and the alkoxy group is an alkoxy group having 1 to 4 carbon atoms [3- (Dialkylamino) propyl] alkoxysilane is preferred.

  Further, the compound containing an alkoxysilyl group may contain a nitrogen atom and a group represented by> C═O. Tris [3- (trimethoxysilyl) propyl] isocyanurate, tris [3- (triethoxysilyl) propyl are compounds containing an alkoxysilyl group and a nitrogen atom and a group represented by> C═O. And tris [(alkoxysilyl) alkyl] isocyanurate compounds such as isocyanurate, tris [3- (tripropoxysilyl) propyl] isocyanurate, and tris [3- (tributoxysilyl) propyl] isocyanurate. Among them, tris [3- (trialkoxysilyl) propyl] isocyanurate is preferable, tris [3- (trialkoxysilyl) propyl] isocyanurate in which the alkoxy group is an alkoxy group having 1 to 4 carbon atoms is more preferable, and tris [ 3- (Trimethoxysilyl) propyl] isocyanurate is more preferred.

  The following compounds (I) and (II) are added to the monomer component in the order of compound (I) and compound (II), and the active end of the polymer formed by polymerizing the monomer component and It is considered that the active terminal of the compound has an alkali metal derived from the organoalkali metal compound of compound (I).) The reaction with the compound containing a nitrogen atom and / or a silicon atom is carried out by reacting with the nitrogen atom. And / or a compound containing a silicon atom is added to the polymerization solution, and the polymer and the compound containing a nitrogen atom and / or silicon atom are mixed in the solution. The amount of the compound containing a nitrogen atom and / or silicon atom added to the polymerization solution is usually 0.1 mol to 3 mol per mol of the organic alkali metal compound of compound (I), preferably It is 5 mol-2 mol, More preferably, it is 0.7 mol-1.5 mol.

  The temperature at which the polymer and the compound containing a nitrogen atom and / or silicon atom are mixed is 25 ° C to 100 ° C, preferably 35 ° C to 90 ° C, and more preferably 50 ° C to 80 ° C. The contact time is 60 seconds to 5 hours, preferably 5 minutes to 1 hour.

  In the production method of the present invention, a coupling agent may be added to a solution containing a conjugated diene polymer using a hydrocarbon as a solvent from the start of polymerization of the monomer to the recovery of the polymer described later. . An example of the coupling agent is a compound represented by the following formula (4).

R ⁴¹ _a ML _4-a (4)
Wherein R ⁴¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents an integer of 0 to 2. Represents.)

  As the coupling agent represented by the above formula (4), silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, Examples thereof include methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.

  The addition amount of the coupling agent is preferably 0.03 mol or more, more preferably 0.05 mol or more, per 1 mol of alkali metal derived from the alkali metal catalyst in order to improve the processability of the conjugated diene polymer. It is. Moreover, in order to improve fuel-saving property, Preferably it is 0.4 mol or less, More preferably, it is 0.3 mol or less.

  In the production method of the present invention, the unreacted active terminal may be treated with an alcohol such as methanol or isopropyl alcohol before the recovery of the polymer described later.

  As a method for recovering a conjugated diene polymer from a solution containing a conjugated diene polymer using a hydrocarbon as a solvent, a known method can be used. For example, (A) a solution containing a conjugated diene polymer can be used. Examples thereof include a method of adding a coagulant and (B) a method of adding steam to a solution containing a conjugated diene polymer. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

  The conjugated diene polymer of the present invention is a conjugated diene polymer produced by the above method.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer of the present invention is preferably 10 or more, more preferably 20 or more, in order to increase the tensile strength at break. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K6300 (1994).

  The molecular weight distribution of the conjugated diene polymer of the present invention is preferably 1 to 5 and more preferably 1 to 2 in order to improve fuel economy. The molecular weight distribution is determined by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

  The content of the monomer unit based on the silicon-containing vinyl compound is preferably 0.01% by weight or more, more preferably 0.02 per 100% by weight of the conjugated diene polymer in order to improve fuel economy. % By weight or more, more preferably 0.05% by weight or more. In order to increase economy and to increase the tensile strength at break, the content is preferably 20% by weight or less, more preferably 2% by weight or less, and further preferably 1% by weight or less.

  In order to increase the tensile strength at break, the conjugated diene polymer of the present invention includes a monomer unit based on an aromatic vinyl compound in addition to a monomer unit based on a conjugated diene compound and a monomer unit based on a silicon-containing vinyl compound. It is preferable to contain. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like, and styrene is preferable.

  The content of the aromatic vinyl compound unit is 0% by weight or more (the content of the conjugated diene compound unit is 100% by weight or less), where the total amount of the conjugated diene compound unit and the aromatic vinyl compound unit is 100% by weight. The content is preferably 10% by weight or more (the content of the conjugated diene compound unit is 90% by weight or less), more preferably 15% by weight or more (the content of the conjugated diene compound unit is 85% by weight or less). In order to improve fuel economy, the content of the aromatic vinyl compound unit is preferably 50% by weight or less (the content of the conjugated diene compound unit is 50% by weight or more), more preferably 45% by weight or less. (The content of the conjugated diene compound unit is 55% by weight or more).

The vinyl bond content of the conjugated diene polymer of the present invention is preferably 80 mol% or less, more preferably 70 mol% or less, in order to improve fuel economy, with the content of the conjugated diene unit being 100 mol%. It is. Moreover, in order to improve grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

  The conjugated diene polymer of the present invention can be used as a conjugated diene polymer composition by blending other polymer components and additives.

  Examples of other polymer components include styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and butyl rubber. Moreover, natural rubber, an ethylene-propylene copolymer, an ethylene-octene copolymer, etc. can be mentioned. One or more of these polymer components are used.

  When other polymer components are blended with the conjugated diene polymer of the present invention, the blended amount of the conjugated diene polymer of the present invention is the total blended amount of the polymer components (conjugated diene) in order to improve fuel economy. 100 weight%), preferably 10 weight% or more, more preferably 20 weight% or more.

  Known additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide; reinforcing agents such as silica and carbon black; calcium carbonate and talc Examples thereof include fillers such as alumina, clay, aluminum hydroxide and mica; silane coupling agents; extension oils; processing aids; anti-aging agents;

  Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The amount of sulfur is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, and further preferably 0.5 parts by weight per 100 parts by weight of the polymer component. Parts to 5 parts by weight.

  Examples of the vulcanization accelerator include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram Thiuram vulcanization accelerators such as disulfide; N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide, N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine It can be mentioned the guanidine-based vulcanization accelerator. The blending amount of the vulcanization accelerator is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight per 100 parts by weight of the polymer component.

Examples of the silica include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. One or more of these can be used. BET specific surface area of silica is ^{preferably, 50m 2 / g~250m 2 / g} . The BET specific surface area is measured according to ASTM D1993-03. As a commercial item, the product name Ultrasil VN3-G by a Degussa company, the product name VN3, AQ, ER, RS-150, the product name by Rhodia company name Zeosil 1115MP, 1165MP, etc. by Tosoh silica company, etc. can be used.

  Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Carbon blacks include channel carbon blacks such as EPC, MPC and CC; furnace carbon blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; FT and MT Thermal carbon black such as acetylene carbon black is exemplified. One or more of these can be used.

Nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably in the 5m ² / g~200m ² / g, also carbon black dibutyl phthalate (DBP) absorption is preferably 5 ml / 100 g to 300 ml / 100 g. The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93. As a commercial item, Mitsubishi Chemical Corporation trade name Dia Black N339, Tokai Carbon Co., Ltd. trade name SHIEST 6, SEAST 7HM, SEAST KH, Degussa trade name CK 3, Special Black 4A, etc. can be used.

  When a conjugated diene polymer composition in which a reinforcing agent is blended with the conjugated diene polymer of the present invention, the blending amount of the reinforcing agent is preferably 100 parts by weight of the blending amount of the conjugated diene polymer of the present invention. Is 10 to 150 parts by weight. The blending amount is more preferably 20 parts by weight or more, and still more preferably 30 parts by weight or more in order to increase the wear resistance and strength. Moreover, in order to improve reinforcement, More preferably, it is 120 weight part or less, More preferably, it is 100 weight part or less.

  When a conjugated diene polymer composition obtained by blending a reinforcing agent with the conjugated diene polymer of the present invention is used, it is preferable to use silica as the reinforcing agent in order to improve fuel economy. As a compounding quantity of a silica, the total compounding quantity of a reinforcing agent is 100 weight part, Preferably it is 50 weight part or more, More preferably, it is 70 weight part or more.

  The weight ratio between the content of silica used as a reinforcing agent and the content of carbon black (silica content: carbon black content) is preferably 2: 1 to 50: 1. The weight ratio is more preferably 5: 1 to 20: 1 in order to enhance fuel economy and enhance reinforcement.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxy Cyril) Pills) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, and the like .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide. One or more of these are used. As a commercial item, Degussa company name Si69, Si75, etc. can be used.

  When it is set as the conjugated diene polymer composition which mix | blended the silane coupling agent with the conjugated diene polymer of this invention, the compounding quantity of a silane coupling agent is based on 100 weight part of silica, Preferably it is 1 weight part-20 weight. Part, more preferably 2 to 15 parts by weight, and still more preferably 5 to 10 parts by weight.

  Examples of the extending oil include aromatic mineral oil (viscosity specific gravity constant (VGC value) 0.900 to 1.049), naphthenic mineral oil (VGC value 0.850 to 0.899), paraffinic mineral oil (VGC value 0.790 to 0.849), and the like. The polycyclic aromatic content of the extender oil is preferably less than 3% by weight, more preferably less than 1% by weight. The polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method. Moreover, the aromatic compound content (CA) of the extending oil is preferably 20% by weight or more. One or more of these extending oils are used.

  As a method for producing a conjugated diene polymer composition by blending the conjugated diene polymer of the present invention with other polymer components or additives, a known method, for example, each component of a roll or Banbury is used. A kneading method using such a known mixer can be used.

  As the kneading conditions, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 ° C. to 200 ° C., preferably 80 ° C. to 190 ° C., and the kneading time is usually 30 seconds to 30 minutes, preferably 1 minute to 30 minutes. When blending a vulcanizing agent and a vulcanization accelerator, the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C. A composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

  The conjugated diene-based polymer composition of the present invention is excellent in fuel economy, tensile strength at break, and grip properties. The conjugated diene polymer composition of the present invention is suitably used for tires.

  The physical properties were evaluated by the following method.

1. Mooney viscosity (ML _{1 + 4} )
According to JIS K6300 (1994), the Mooney viscosity of the polymer was measured at 100 ° C.

2. Vinyl bond amount (unit: mol%)
The amount of vinyl bonds in the polymer was determined from the absorption intensity near 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

3. Styrene unit content (unit:% by weight)
According to JIS K6383 (1995), the content of styrene units in the polymer was determined from the refractive index.

4). Molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8), and the molecular weight distribution (Mw / Mn) was determined.

(1) Equipment: HLC-8220 manufactured by Tosoh Corporation
(2) Separation column: Tosoh TSKgel SuperHM-H (two in series)
(3) Measurement temperature: 40 ℃
(4) Carrier: Tetrahydrofuran
(5) Flow rate: 0.6mL / min
(6) Injection volume: 5μL
(7) Detector: Differential refraction
(8) Molecular weight standard: Standard polystyrene

5. Fuel saving performance A test piece on a strip having a width of 1 mm or 2 mm and a length of 40 mm was punched out of a sheet-like vulcanized molded article and used for the test. In the measurement, the loss tangent (tan δ (70 ° C.)) of the test piece at a temperature of 70 ° C. was measured with a viscoelasticity measuring apparatus (manufactured by Ueshima Seisakusho Co., Ltd.) under the conditions of 1% strain and 10 Hz frequency. The smaller this value, the better the fuel economy.

6). Grip property A test piece on a strip having a width of 1 mm or 2 mm and a length of 40 mm was punched out from a sheet-like vulcanized molded article and used for the test. The measurement was performed by measuring the loss tangent (tan δ (0 ° C.)) of the test piece at a temperature of 0 ° C. under the conditions of a strain of 2.5% and a frequency of 10 Hz using a viscoelasticity measuring apparatus (manufactured by Ueshima Seisakusho). The larger this value, the better the grip.

7). Tensile strength at break (TB, unit: MPa)
According to JIS K6251, a No. 3 type dumbbell test piece was used, the tensile rate was 500 mm / min, and the stress when the test piece broke was measured.

Example 1
The inside of a stainless steel polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 6.1 ml of tetrahydrofuran, and 5.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium n-hexane solution was charged into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.

  2.74 g of bis (diethylamino) methylvinylsilane was charged into the polymerization reactor. Next, an n-hexane solution of n-butyllithium (content of n-butyllithium 15.4 mmol) was charged into the polymerization reactor as a polymerization initiator component, and immediately afterwards 1.09 g (n-butyllithium) of pyrrolidine. 1.01 mol per mol) was charged into the polymerization reactor to start the polymerization reaction. 1,3-butadiene, styrene, and bis (diethylamino) methyl while stirring speed is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. Vinylsilane copolymerization was carried out for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 912 g and 288 g, respectively. In the total amount of monomers charged or supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.14% by weight.

  20 ml of hexane solution containing 1.2 ml of methanol was added to the polymerization solution, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 4.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours, Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 1.

  100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization acceleration 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.4 parts by weight of sulfur, Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. The physical property evaluation results of the vulcanized sheet are shown in Table 1.

Example 2
The inside of a stainless steel polymerization reactor with an internal volume of 30 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 15.3 kg of industrial hexane (density 680 kg / m ³ ), 912 g of 1,3-butadiene, 288 g of styrene, 9.1 ml of tetrahydrofuran, and 7.8 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium n-hexane solution was charged into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.

  Bis (diethylamino) methylvinylsilane (4.12 g) was charged into the polymerization reactor. Thereafter, n-hexane solution of n-butyllithium (content of n-butyllithium 23.1 mmol) was charged into the polymerization reactor as a polymerization initiator component. 1.01 mol per mol of lithium) was charged into the polymerization reactor to initiate the polymerization reaction. 1,3-butadiene, styrene, and bis (diethylamino) methyl while stirring speed is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. Vinylsilane copolymerization was carried out for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 1368 g and 432 g, respectively. In the total amount of monomers charged or supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.14% by weight.

  To the polymerization solution, 20 ml of a hexane solution containing 1.5 ml of methanol was added, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 6.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours. Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 1.

  100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization acceleration 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.4 parts by weight of sulfur, Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. The physical property evaluation results of the vulcanized sheet are shown in Table 1.

Comparative Example 1
The inside of a stainless steel polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 6.1 ml of tetrahydrofuran, and 4.4 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium solution in n-butyllithium was charged into the polymerization vessel as a scavenger in order to detoxify impurities that act on the deactivation of the polymerization initiator in advance.

  2.63 g of bis (diethylamino) methylvinylsilane was charged into the polymerization reactor, and then n-hexane solution of n-butyllithium (content of n-butyllithium 12.3 mmol) was used as the polymerization initiator component. The polymerization reaction was started. While stirring speed is 130 rpm, polymerization reactor internal temperature is 65 ° C. and 1,3-butadiene and styrene are continuously fed into the polymerization reactor, 1,3-butadiene, styrene and bis (diethylamino) The copolymerization reaction of methyl vinyl silane was performed for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 912 g and 288 g, respectively. In the total amount of monomers charged or supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.13% by weight.

  20 ml of hexane solution containing 0.8 ml of methanol was added to the polymerization solution, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 4.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours. Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 1.

  100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization acceleration 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.4 parts by weight of sulfur, Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. The physical property evaluation results of the vulcanized sheet are shown in Table 1.

Comparative Example 2
The inside of a stainless steel polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 6.1 ml of tetrahydrofuran, and 5.2 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium n-hexane solution was charged into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.

  As a polymerization initiator, an n-hexane solution of n-butyllithium (content of n-butyllithium 15.6 mmol) was charged into the polymerization reactor, and immediately afterwards 1.11 g of pyrrolidine (1.01 mol per mol of n-butyllithium). ) Was introduced into the polymerization reactor to initiate the polymerization reaction. While the stirring speed is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor, the copolymerization reaction of 1,3-butadiene and styrene is performed. I went for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 912 g and 288 g, respectively.

  To the polymerization solution was added 20 ml of a hexane solution containing 1.0 ml of methanol, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 4.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours. Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 1.

  100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization acceleration 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.4 parts by weight of sulfur, Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. The physical property evaluation results of the vulcanized sheet are shown in Table 1.

Comparative Example 3
The inside of a stainless steel polymerization reactor with an internal volume of 30 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 15.3 kg of industrial hexane (density 680 kg / m ³ ), 912 g of 1,3-butadiene, 288 g of styrene, 9.1 ml of tetrahydrofuran, and 8.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium n-hexane solution was charged into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.

  As a polymerization initiator, an n-hexane solution of n-butyllithium (a content of n-butyllithium of 22.2 mmol) was charged into the polymerization reactor, and immediately thereafter 2.20 g of hexamethyleneimine (per mol of n-butyllithium). 1.01 mol) was charged into the polymerization reactor to initiate the polymerization reaction. While the stirring speed is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor, the copolymerization reaction of 1,3-butadiene and styrene is performed. I went for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 1368 g and 432 g, respectively.

  20 ml of hexane solution containing 1.4 ml of methanol was added to the polymerization solution, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 6.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours, Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 1.

100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ), 1 part by weight 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.) Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. The physical property evaluation results of the vulcanized sheet are shown in Table 1.

Example 3
The inside of a stainless steel polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 6.1 ml of tetrahydrofuran, and 5.5 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium n-hexane solution was charged into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.

  2.74 g of bis (diethylamino) methylvinylsilane was charged into the polymerization reactor. Next, an n-hexane solution of n-butyllithium (content of n-butyllithium: 17.1 mmol) was charged into the polymerization reactor as a polymerization initiator component, and then 1.22 g (n-butyllithium) of pyrrolidine was immediately added. 1.02 mol per 1 mol) was added to initiate the polymerization reaction. 1,3-butadiene, styrene, and bis (diethylamino) methyl while stirring speed is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. Vinylsilane copolymerization was carried out for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 912 g and 288 g, respectively. In the total amount of monomers charged or supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.14% by weight.

  Next, the obtained polymerization solution was stirred at a stirring speed of 130 rpm, 17.1 mmol of N- (3-dimethylaminopropyl) acrylamide was added to the polymerization solution, and stirred for 15 minutes.

  20 ml of hexane solution containing 1.2 ml of methanol was added to the polymerization solution, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 4.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours. Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 2.

  100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization acceleration 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.4 parts by weight of sulfur, Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. Table 2 shows the physical property evaluation results of the vulcanized sheet.

Example 4
The inside of a stainless steel polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 6.1 ml of tetrahydrofuran, and 5.1 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium n-hexane solution was charged into the polymerization reactor as a scavenger in order to detoxify impurities that act to deactivate the polymerization initiator in advance.

  2.74 g of bis (diethylamino) methylvinylsilane was charged into the polymerization reactor. Next, an n-hexane solution of n-butyllithium (content of n-butyllithium 13.0 mmol) was charged into the polymerization reactor as a polymerization initiator component, and immediately after that, 1.11 g of piperidine (n-butyllithium). 1.00 mol) per mol, and the polymerization reaction was started. 1,3-butadiene, styrene, and bis (diethylamino) methyl while stirring speed is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. Vinylsilane copolymerization was carried out for 3 hours. The amounts of 1,3-butadiene and styrene supplied after the start of the polymerization reaction were 912 g and 288 g, respectively. In the total amount of monomers charged or supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.14% by weight.

  Next, the obtained polymerization solution was stirred at a stirring speed of 130 rpm, and 13.02 mmol of N- (3-dimethylaminopropyl) acrylamide was added to the polymerization solution, followed by stirring for 15 minutes.

  To the polymerization solution was added 20 ml of a hexane solution containing 1.0 ml of methanol, and the polymerization solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymerization solution. 0 g, 4.0 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization solution was allowed to stand at room temperature for 24 hours. Was evaporated to obtain a polymer. Thereafter, the obtained polymer was further dried under reduced pressure at 55 ° C. for 12 hours. The evaluation results of the polymer are shown in Table 2.

100 parts by weight of the obtained polymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69), 6.4 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd., trade name: Diamond Black N339), 47.6 parts by weight of extension oil (Japan Energy Co., Ltd., trade name: JOMO Process NC-140), anti-aging agent (Sumitomo Chemical) Product name: Antigen 3C) 1.5 parts by weight, stearic acid 2 parts by weight, zinc white 2 parts by weight, vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulcanization acceleration 1 part by weight of an agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Soxinol D), 1.5 parts by weight of wax (trade name: Sannok N, produced by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.4 parts by weight of sulfur, Kneading in , To prepare a polymer composition. The obtained polymer composition was formed into a sheet with a 6-inch roll, and the sheet was heated and vulcanized at 160 ° C. for 45 minutes to prepare a vulcanized sheet. Table 2 shows the physical property evaluation results of the vulcanized sheet.

Claims (7)

The following compounds (I) and (II) as a polymerization initiator component are added in the order of compound (I) and compound (II) to a solution containing a hydrocarbon as a solvent and at least one monomer component, A method for producing a conjugated diene polymer, wherein a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound is polymerized.
(I) Organic alkali metal compound (II) Compound represented by the following formula (1)

(In the formula, R ¹¹ represents a hydrocarbylene group having 3 to 20 carbon atoms which may have at least one atom selected from the group consisting of silicon atom, nitrogen atom and oxygen atom as a hetero atom. .)   The method for producing a conjugated diene polymer according to claim 1, wherein the compound (II) is added to the solution while the polymerization conversion rate of the monomer component is 5% by weight or less.   The amount of the compound (II) added while the polymerization conversion rate of the monomer component is 5% by weight or less is 0.5 mol to 2.0 mol with respect to 1 mol of the compound (I) added. A process for producing a conjugated diene polymer as described in 1.   The method for producing a conjugated diene polymer according to any one of claims 1 to 3, wherein a compound containing a nitrogen atom and / or a silicon atom is reacted with an active terminal of a polymer produced by polymerization.   The method for producing a conjugated diene polymer according to claim 4, wherein the compound containing a nitrogen atom and / or a silicon atom is a compound containing a nitrogen atom and a carbonyl group.   A conjugated diene polymer produced by the method according to claim 1.   A conjugated diene polymer comprising the conjugated diene polymer according to claim 6 and a reinforcing agent, wherein the content of the reinforcing agent is 10 to 150 parts by weight per 100 parts by weight of the conjugated diene polymer. Composition.