JP2013209462A - Conjugated diene polymer, polymer composition, and method for producing conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a conjugated diene polymer which is usable in preparation of a polymer composition being excellent in fuel consumption-saving property; a polymer composition containing the conjugated diene polymer and a reinforcing member; and a method for producing conjugated diene polymer.SOLUTION: A conjugated diene polymer comprises a monomer unit derived from a conjugated diene, a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom via a hydrocarbylene group.

Description

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

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

  For example, Patent Document 1 discloses a conjugated diene polymer obtained by living anionic polymerization of butadiene, styrene, and bis (diethylamino) methylvinylsilane using alkyllithium as a polymerization initiator, and the polymer and a reinforcing material. A polymer composition containing is described. Patent Document 2 discloses a conjugated diene polymer obtained by living anion polymerization of butadiene, styrene, and dimethyl-1-piperidinylmethylvinylsilane using alkyllithium as a polymerization initiator, and the polymer and reinforcing material. Polymer compositions containing are described.

JP 2010-77386 A JP 2011-208012 A

  However, a polymer composition using the above-mentioned conventional conjugated diene polymer is not always satisfactory in terms of fuel economy.

  Under such circumstances, the problem to be solved by the present invention is a conjugated diene polymer useful for the preparation of a polymer composition having excellent fuel economy, and a heavy polymer containing the conjugated diene polymer and a reinforcing material. The object is to provide a coalescence composition and a method for producing the conjugated diene polymer.

  The first of the present invention is a monomer unit derived from a conjugated diene, a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, The present invention relates to a conjugated diene polymer having a monomer unit derived from a silicon-containing vinyl monomer bonded to a silicon atom via a carbylene group.

  2nd of this invention contains said conjugated diene polymer and a reinforcing material, and content of a reinforcing material is 10 to 150 weight part with respect to 100 weight part of conjugated diene polymer. It relates to a certain polymer composition.

  In the third aspect of the present invention, a conjugated diene, a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a substituted amino group are hydrocarbylene groups in a hydrocarbon solvent by an alkali metal catalyst. It is a manufacturing method of the conjugated diene polymer which polymerizes the monomer component containing the silicon-containing vinyl-type monomer couple | bonded with the silicon atom through this.

  According to the present invention, it is possible to obtain a conjugated diene polymer useful for the preparation of a polymer composition excellent in fuel economy and grip properties, and a polymer composition containing the conjugated diene polymer and a reinforcing material. .

  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. The substituted hydrocarbylene group having an oxygen atom as a hetero atom is a group in which at least one carbon atom and / or hydrogen atom other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed is replaced with a group having an oxygen atom. Represents a divalent group having the above structure.

[Conjugated diene polymer]
The conjugated diene polymer of the present invention includes a monomer unit derived from a conjugated diene, a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a substituted amino group. And a monomer unit derived from a silicon-containing vinyl monomer in which a group is bonded to a silicon atom via a hydrocarbylene group.

<Conjugated dienes>
Examples of the conjugated diene 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.

<Silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom>
Examples of the silicon-containing vinyl monomer in which the substituted amino group is bonded to a silicon atom include a compound represented by the following formula (1).
R ¹¹ SiA ¹ _m R ¹² _3-m (1)
(Wherein, R ¹¹ is a polymerizable carbon - represents a hydrocarbyl group having a carbon double bond, A ¹ represents a substituted amino group, if A ¹ is more, even more certain A ¹ is the same respectively may be different, R ¹² represents a hydrocarbyl group, if R ¹² is plural, plural R ¹² may be different even in the same, respectively, m is an integer of 1-3.)

  In the formula (1), m is an integer of 1 to 3, preferably 1 or 2, and more preferably 2.

（式中、ｋは０又は１であり、Ｘ¹はヒドロカルビレン基を表す。） In the formula (1), examples of the hydrocarbyl group having a polymerizable carbon-carbon double bond represented by R ¹¹ include a group represented by the following formula (1-A).

(In the formula, k is 0 or 1, and X ¹ represents a hydrocarbylene group.)

In the formula (1-A), examples of the hydrocarbylene group represented by X ¹ include an arylene group and an alkenediyl group. As the arylene group, a phenylene group can be exemplified. Examples of alkenediyl groups include vinylene groups and vinylidene groups.

Of the groups represented by the formula (1-A), preferred groups are a vinyl group in which k is 0, a 4-vinylphenyl group in which k is 1 and X ¹ is a phenylene group, and k is 1. An example is a 1-methylene-2-propenyl group in which X ¹ is a vinylidene group.

  The group represented by the formula (1-A) is more preferably a vinyl group.

（式中、Ｘ²及びＸ³は、それぞれ、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、Ｘ²はＸ³に結合しており、Ｘ²がＸ³に結合した基が酸素原子を有していてもよいヒドロカルビレン基を表す。） In the formula (1), examples of the substituted amino group represented by A ¹ include a substituted amino group represented by the following formula (1-B).

(Wherein, X ² and X ³ are each a hydrocarbyl group, or, or represents a trihydrocarbylsilyl group, or, X ² is linked to X ^3, oxygen radical X ² is bonded to X ³ It represents a hydrocarbylene group which may have an atom.)

In the formula (1-B), examples of the hydrocarbyl group of X ² and X ³ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl 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. Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group and isopropenyl group. An ethynyl group can be mentioned as an alkynyl group. A phenyl group can be mentioned as an aryl group. A benzyl group can be mentioned as an aralkyl group.

The number of carbon atoms of the hydrocarbyl group of X ² and X ³ is preferably 1 to 10, more preferably 1 to 4.

The hydrocarbyl group of X ² and X ³ is preferably an alkyl group, more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group represented by X ² and X ³ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyl-dimethylsilyl group.

The trihydrocarbylsilyl group represented by X ² and X ³ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

The hydrocarbylene group which may have an oxygen atom in the group in which X ² is bonded to X ³ represents a hydrocarbylene group or a substituted hydrocarbylene group having an oxygen atom as a hetero atom. Examples of the hydrocarbylene group include an alkylene group, and examples of the alkylene group include polymethylene groups such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the substituted hydrocarbylene group having an oxygen atom as a hetero atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group in which X ² is bonded to X ³ is preferably 2 to 20, more preferably 3 to 8, and further preferably 4 to 6.

The hydrocarbylene group which may have an oxygen atom in the group in which X ² is bonded to X ³ is preferably a hydrocarbylene group, more preferably an alkylene group, still more preferably a polymethylene group. is there.

Examples of the substituted amino group represented by the formula (1-B) include an acyclic substituted amino group and a cyclic substituted amino group. The acyclic substituted amino group is a substituted amino group in which X ² and X ³ are a hydrocarbyl group or a trihydrocarbylsilyl group in the formula (1-B), and the cyclic substituted amino group is a formula (1-B) In the above, the group in which X ² is bonded to X ³ and X ² is bonded to X ³ is a substituted amino group which is a hydrocarbylene group which may have an oxygen atom.

Among the acyclic substituted amino groups, those in which X ² and X ³ are hydrocarbyl groups in the formula (1-B) include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a diisopropyl group, Examples thereof include dialkylamino groups such as -n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, and ethylmethylamino group.
Among the acyclic amino groups, in formula (1-B), X ² and X ³ are trihydrocarbylsilyl groups such as bis (trimethylsilyl) amino group, bis (tert-butyl-dimethylsilyl) amino group, etc. A bis (trialkylsilyl) amino group can be mentioned.

Among cyclic substituted amino group, in the formula (1-B), X ² is bonded to X ^3, as a group X ² is bonded to X ³ is a hydrocarbylene group, the 1-aziridinyl Group, 1-azetidinyl group, 1-pyrrolidinyl group, piperidino group, 1-hexamethyleneimino group.
Among the cyclic substituted amino groups, in the formula (1-B), a group in which X ² is bonded to X ³ and X ² is bonded to X ³ is a substituted hydrocarbylene group having an oxygen atom as a hetero atom. Some include morpholino groups.

The substituted amino group of A ^{1 in} formula (1) is preferably a substituted amino group represented by formula (1-B). More preferably, it is a substituted amino group represented by the formula (1-B), wherein X ² and X ³ in the formula (1-B) are a linear alkyl group or a trialkylsilyl group. is a group, or X ² is bound to X ^3, group X ² is bonded to X ³ is cyclic substituted amino group is a polymethylene group.

More preferably, the substituted amino group of A ^{1 in} the formula (1) is a substituted amino group represented by the formula (1-B), wherein X ² and X ³ are linear alkyl groups. And particularly preferably a dimethylamino group, a diethylamino group, a di-n-propylamino group, or a di-n-butylamino group.

Examples of the R ¹² hydrocarbyl group of the formula (1) include an alkyl group. Examples of the alkyl 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, and a methyl group is preferable.

In the formula (1), the number of carbon atoms of the hydrocarbyl group represented by R ¹² is preferably 1 to 4, more preferably 1.

Among the compounds represented by the formula (1), R ¹¹ is a vinyl group, R ¹² is a methyl group, A ¹ is a substituted amino group represented by the formula (1-B), and X ² Examples of the compound in which X ³ is a non-cyclic substituted amino group which is a linear alkyl group include the following compounds.

Compound in which m in formula (1) is 1:
(Dimethylamino) dimethylvinylsilane,
(Diethylamino) dimethylvinylsilane,
(Di-n-propylamino) dimethylvinylsilane,
(Di-n-butylamino) dimethylvinylsilane.

Compound in which m in formula (1) is 2:
Bis (dimethylamino) methylvinylsilane,
Bis (diethylamino) methylvinylsilane,
Bis (di-n-propylamino) methylvinylsilane,
Bis (di-n-butylamino) methylvinylsilane.

Among the compounds represented by the formula (1), R ¹¹ is a vinyl group, R ¹² is an ethyl group, A ¹ is represented by the formula (1-B), and X in the formula (1-B) Examples of the compound in which ² and X ³ are acyclic substituted amino groups that are linear alkyl groups include the following compounds.

Compound in which m in formula (1) is 1:
(Dimethylamino) diethylvinylsilane,
(Diethylamino) diethylvinylsilane,
(Di-n-propylamino) diethylvinylsilane,
(Di-n-butylamino) diethylvinylsilane.

Compound in which m in formula (1) is 2:
Bis (dimethylamino) ethylvinylsilane,
Bis (diethylamino) ethylvinylsilane,
Bis (di-n-propylamino) ethylvinylsilane,
Bis (di-n-butylamino) ethylvinylsilane.

The silicon-containing vinyl monomer in which the substituted amino group is bonded to the silicon atom is preferably a compound represented by the above formula (1),
More preferably, it is a compound represented by the above formula (1), wherein in the above formula (1), R ¹¹ is a group represented by the formula (1-A), and A ¹ is the formula (1-B). A substituted amino group represented by:
More preferably, it is a compound represented by the above formula (1), wherein R ¹¹ is a vinyl group, R ¹² is an alkyl group having 1 to 4 carbon atoms, and m is 1 or 2, a substituted amino group in which a ¹ is represented by the formula (1-B), is a non-cyclic substituted amino group X ² and X ³ is an alkyl group having 1 to 10 carbon atoms A compound,
Most preferably, it is a compound represented by the above formula (1), wherein R ¹¹ is a vinyl group, R ¹² is a methyl group, m is 2, and A ¹ is a formula represented by the above formula (1). A substituted amino group represented by (1-B), wherein X ² and X ³ are non-cyclic substituted amino groups which are linear alkyl groups having 1 to 4 carbon atoms;
Particularly preferably,
Bis (dimethylamino) methylvinylsilane,
Bis (diethylamino) methylvinylsilane,
Bis (di-n-propylamino) methylvinylsilane,
Or bis (di-n-butylamino) methylvinylsilane.

<Silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom via a hydrocarbylene group>
Examples of the silicon-containing vinyl monomer in which the substituted amino group is bonded to the silicon atom via a hydrocarbylene group include a compound represented by the following formula (2).
R ²¹ Si (-R ²² -A ² ) _n R ²³ _3-n (2)
(Wherein, R ²¹ is a polymerizable carbon - represents a hydrocarbyl group having a carbon double bond, R ²² represents a hydrocarbylene group, if R ²² is plural, a plurality of R ²² are the same respectively may also be different, a ² represents a substituted amino group, if a ² there is a plurality, a plurality of a ² may be different even in the same, respectively, R ²³ represents a hydrocarbyl radical, R ^When there are a plurality of ²³ , the plurality of R ²³ may be the same or different, and n represents an integer of 1 to 3.)

  In the formula (2), n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

（式中、ｐは０又は１であり、Ｙ¹はヒドロカルビレン基を表す。） In the formula (2), examples of R ²¹ include a group represented by the following formula (2-A).

(In the formula, p is 0 or 1, and Y ¹ represents a hydrocarbylene group.)

In the formula (2-A), examples of the hydrocarbylene group for Y ¹ include an arylene group and an alkenediyl group. As the arylene group, a phenylene group can be exemplified. Examples of alkenediyl groups include vinylene groups and vinylidene groups.

Preferred groups represented by the formula (2-A) include a vinyl group in which p is 0, a 4-vinylphenyl group in which p is 1 and Y ¹ is a phenylene group, p is 1 and Y ¹ is vinylidene. And 1-methylene-2-propenyl group which is a group.

  The group represented by the formula (2-A) is more preferably a vinyl group.

In the formula (2), examples of the hydrocarbylene group represented by R ²² include a methylene group and an alkylene group. Examples of the alkylene group include polymethylene groups such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. The group can be mentioned.

In the formula (2), the number of carbon atoms of the hydrocarbylene group represented by R ²² is preferably 1 or 3, and more preferably 1.

In the formula (2), the hydrocarbylene group represented by R ²² is preferably a methylene group or a trimethylene group, and more preferably a methylene group.

（式中、Ｙ²及びＹ³は、それぞれ、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、Ｙ²はＹ³に結合しており、Ｙ²がＹ³に結合した基が酸素原子を有していてもよいヒドロカルビレン基を表す。） In formula (2), examples of the substituted amino group represented by A ² include substituted amino groups represented by the following formula (2-B).

(Wherein, Y ² and Y ³ are each a hydrocarbyl group, or, or represents a trihydrocarbylsilyl group, or, Y ² is bonded to Y ^3, oxygen radical Y ² is bonded to Y ³ It represents a hydrocarbylene group which may have an atom.)

In the formula (2-B), examples of the hydrocarbyl group of Y ² and Y ³ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl 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. Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group and isopropenyl group. An ethynyl group can be mentioned as an alkynyl group. A phenyl group can be mentioned as an aryl group. A benzyl group can be mentioned as an aralkyl group.

The number of carbon atoms of the hydrocarbyl group of Y ² and Y ³ is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 to 2.

The hydrocarbyl group of Y ² and Y ³ is preferably an alkyl group, more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group represented by Y ² and Y ³ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyl-dimethylsilyl group.

The trihydrocarbylsilyl group of Y ² and Y ³ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

The hydrocarbylene group which may have an oxygen atom in the group in which Y ² is bonded to Y ³ represents a hydrocarbylene group or a substituted hydrocarbylene group having an oxygen atom as a hetero atom. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the substituted hydrocarbylene group having an oxygen atom as a hetero atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group in which Y ² is bonded to Y ³ is preferably 2 to 20, more preferably 3 to 8, and further preferably 4 to 6.

In the group in which Y ² is bonded to Y ³ , the hydrocarbylene group which may have an oxygen atom is preferably a hydrocarbylene group, more preferably an alkylene group, still more preferably a polymethylene group. is there.

Examples of the substituted amino group represented by the formula (2-B) include an acyclic substituted amino group and a cyclic substituted amino group. The acyclic substituted amino group is a substituted amino group in which Y ² and Y ³ are a hydrocarbyl group or a trihydrocarbylsilyl group in the formula (2-B), and the cyclic substituted amino group is a formula (2-B) in, Y ² is bonded to Y ^3, Y ² is a substituted amino group which is attached groups are hydrocarbylene group optionally having an oxygen atom in Y ^3.

Among the acyclic substituted amino groups, those in which Y ² and Y ³ are hydrocarbyl groups in the formula (2-B) include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a diisopropyl group, Examples thereof include dialkylamino groups such as -n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, and ethylmethylamino group. Among the acyclic amino groups, those in which Y ² and Y ³ are trihydrocarbylsilyl groups in formula (2-B) include bis (trimethylsilyl) amino groups, bis (tert-butyl-dimethylsilyl) amino groups and the like. A bis (trialkylsilyl) amino group can be mentioned.

Among cyclic substituted amino group, in the formula (2-B), Y ² is bonded to Y ^3, as group Y ² is bonded to Y ³ is a hydrocarbylene group, 1-aziridinyl Group, 1-azetidinyl group, 1-pyrrolidinyl group, piperidino group, 1-hexamethyleneimino group.
Among cyclic substituted amino group, in the formula (2-B), Y ² is bonded to Y ^3, substituted hydrocarbylene group Y ² has an oxygen atom as bonded groups heteroatom Y ³ Some include morpholino groups.

The substituted amino group of A ^{2 in} formula (2) is preferably a substituted amino group represented by formula (2-B). More preferably, in formula (2-B), Y ² and Y ³ are non-cyclic substituted amino groups which are linear alkyl groups or trialkylsilyl groups, or Y ² is bonded to Y ³ , Y ² is a cyclic substituted amino group in which the group bonded to Y ³ is a polymethylene group.

More preferably the substituted amino group of A ² in Formula (2), Y ² is bonded to Y ³ in the formula (2-B), cyclic substituted amino group Y ² is bonded to Y ³ is a polymethylene group It is a group. A substituted amino group for A ² is particularly preferably a 1-pyrrolidinyl group, piperidino group, or 1-hexamethyleneimino group.

Examples of the hydrocarbyl group of R ^{23 in} the formula (2) include an alkyl group. Examples of the alkyl 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.

In the formula (1), the number of carbon atoms of the hydrocarbyl group represented by R ²³ is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

The hydrocarbyl group of R ^{23 in} the formula (2) is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group.

Of the compounds represented by formula (2), R ²¹ is a vinyl group, R ²² is a methylene group, R ²³ is a methyl group, and A ² is a substitution represented by formula (2-B). an amino group, Y ² is bonded to Y ^3, Y ² is a compound group attached to Y ³ is a cyclic substituted amino group is a polymethylene group include the following compounds.

Compound in which n in formula (2) is 1:
Dimethyl (1-pyrrolidinylmethyl) vinylsilane,
Dimethyl (piperidinomethyl) vinylsilane,
(1-Hexamethyleneiminomethyl) dimethylvinylsilane.

Compound in which n in formula (2) is 2:
Methylbis (1-pyrrolidinylmethyl) vinylsilane,
Methylbis (piperidinomethyl) vinylsilane,
Bis (1-hexamethyleneiminomethyl) methylvinylsilane.

Of the compounds represented by formula (2), R ²¹ is a vinyl group, R ²² is a methylene group, R ²³ is a methyl group, and A ² is a substitution represented by formula (2-B). Examples of the compound which is an amino group and is an acyclic substituted amino group in which Y ² and Y ³ are linear alkyl groups include the following compounds.

Compound in which n in formula (2) is 1:
(Dimethylaminomethyl) dimethylvinylsilane,
(Diethylaminomethyl) dimethylvinylsilane,
(Di-n-propylaminomethyl) dimethylvinylsilane,
(Di-n-butylaminomethyl) dimethylvinylsilane.

Compound in which n in formula (2) is 2:
Bis (dimethylaminomethyl) methylvinylsilane,
Bis (diethylaminomethyl) methylvinylsilane,
Bis (di-n-propylaminomethyl) methylvinylsilane,
Bis (di-n-butylaminomethyl) methylvinylsilane.

Of the compounds represented by formula (2), R ²¹ is a vinyl group, R ²² is a trimethylene group, R ²³ is a methyl group, and A ² is a substitution represented by formula (2-B). an amino group, Y ² is bonded to Y ^3, Y ² is a compound group attached to Y ³ is a cyclic substituted amino group is a polymethylene group include the following compounds.

Compound in which n in formula (2) is 1:
Dimethyl [3- (1-pyrrolidinyl) propyl] vinylsilane,
Dimethyl (3-piperidinopropyl) vinylsilane,
[3- (1-Hexamethyleneimino) propyl] dimethylvinylsilane.

Compound in which n in formula (2) is 2:
Methylbis [3- (1-pyrrolidinyl) propyl] vinylsilane,
Methylbis (3-piperidinopropyl) vinylsilane,
Bis [3- (1-hexamethyleneimino) propyl] methylvinylsilane.

Of the compounds represented by formula (2), R ²¹ is a vinyl group, A ² is an acyclic substituted amino group, R ²² is a trimethylene group, R ²³ is a methyl group, and A ² Is a substituted amino group represented by the formula (2-B) and Y ² and Y ³ are non-cyclic substituted amino groups which are linear alkyl groups, the following compounds can be exemplified.

Compound in which n in formula (2) is 1:
[3- (dimethylamino) propyl] dimethylvinylsilane,
[3- (diethylamino) propyl] dimethylvinylsilane,
[3- (di-n-propylamino) propyl] dimethylvinylsilane,
[3- (Di-n-butylamino) propyl] dimethylvinylsilane.

Compound in which n in formula (2) is 2:
Bis [3- (dimethylamino) propyl] methylvinylsilane,
Bis [3- (diethylamino) propyl] methylvinylsilane,
Bis [3- (di-n-propylamino) propyl] methylvinylsilane,
Bis [3- (di-n-butylamino) propyl] methylvinylsilane.

The silicon-containing vinyl monomer in which the substituted amino group is bonded to the silicon atom via the hydrocarbylene group is preferably a compound represented by the above formula (2),
More preferably, it is a compound represented by the above formula (2), wherein in the above formula (2), R ²¹ is a group represented by the formula (2-A), and A ² is a formula (2-B). A substituted amino group represented by:
More preferably, it is a compound represented by the above formula (2), wherein in the above formula (2), R ²¹ is a vinyl group, R ²² is a methylene group or a trimethylene group, and R ²³ is 1 carbon atom. a to 4 alkyl group, n is 1 or 2, a substituted amino group in which a ² is represented by the formula (2-B), Y ² is bonded to Y ^3, Y ² is A compound in which the group bonded to Y ³ is a cyclic substituted amino group which is a polymethylene group having 3 to 8 carbon atoms;
Most preferably, it is a compound represented by the above formula (2), wherein in the above formula (2), R ²¹ is a vinyl group, R ²² is a methylene group, and R ²³ is a methyl group or an ethyl group. , N is 1, and A ² is a 1-pyrrolidinyl group, piperidino group, or 1-hexamethyleneimino group,
Particularly preferably,
Dimethyl (1-pyrrolidinylmethyl) vinylsilane,
Dimethyl (piperidinomethyl) vinylsilane,
Or (1-hexamethyleneiminomethyl) dimethylvinylsilane.

  The conjugated diene polymer of the present invention includes a monomer unit derived from a conjugated diene, a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a substituted amino In addition to a monomer unit derived from a silicon-containing vinyl monomer in which the group is bonded to a silicon atom via a hydrocarbylene group, preferably a monomer unit derived from an aromatic vinyl compound is contained. . Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene, and styrene is preferable.

  Among the monomer units contained in the conjugated diene polymer of the present invention, a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a substituted amino group is a hydrocarbyl The total content of monomer units derived from a silicon-containing vinyl monomer bonded to a silicon atom via a group is 100% by weight based on the total amount of monomer units contained in the conjugated diene polymer. In order to improve fuel economy, it is preferably 0.02% by weight or more, more preferably 0.04% by weight or more, and further preferably 0.2% by weight or more. Moreover, in order to improve grip property, Preferably it is 20 weight% or less, More preferably, it is 7 weight% or less, More preferably, it is 3.5 weight% or less.

  An amount of monomer unit derived from a silicon-containing vinyl monomer in which the substituted amino group is bonded to a silicon atom via a hydrocarbyl group, in a silicon-containing vinyl group in which the substituted amino group is bonded to the silicon atom. Weight ratio to the amount of monomer units derived from the monomer (monomer unit / substituted amino group derived from silicon-containing vinyl monomer in which substituted amino group is bonded to silicon atom via hydrocarbyl group) The monomer unit derived from a silicon-containing vinyl monomer bonded to a silicon atom is preferably 10/90 or more, more preferably 20/80, in order to improve fuel economy and grip properties. It is above, Preferably it is 90/10 or less, More preferably, it is 80/20 or less.

  Among the monomer units contained in the conjugated diene polymer of the present invention, the content of monomer units derived from the conjugated diene is 100% by weight of the total amount of monomer units contained in the conjugated diene polymer. Is preferably 40% by weight or more.

  When the conjugated diene polymer of the present invention contains a monomer unit derived from an aromatic vinyl compound, the content of the monomer unit derived from the conjugated diene and the monomer unit derived from the aromatic vinyl The total amount is preferably 99.98% by weight or less, more preferably 99.96% by weight or less, still more preferably 99% by weight, with the total amount of monomer units contained in the conjugated diene polymer as 100% by weight. .8% by weight or less. Further, it is preferably 80% by weight or more, more preferably 93% by weight or more, and further preferably 96.5% by weight or more.

  When the conjugated diene polymer of the present invention contains a monomer unit derived from an aromatic vinyl compound, the monomer unit derived from the aromatic vinyl compound in an amount of the monomer unit derived from the conjugated diene. The weight ratio to the amount of monomer (monomer unit derived from conjugated diene / monomer unit derived from aromatic vinyl compound) is preferably 50/50 or more, more preferably 55 in order to improve fuel economy. / 45 or more. Moreover, in order to improve grip property and tensile strength, Preferably it is 90/10 or less, More preferably, it is 85/15 or less.

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 vinyl bond amount of the conjugated diene polymer of the present invention is preferably 80 mol% or less in order to improve the fuel economy by setting the content of monomer units derived from the conjugated diene to 100 mol%. Preferably it is 70 mol% or less. 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 is preferably a conjugated diene polymer having a nitrogen atom-containing group at at least one polymer chain end.

（Ｒ³¹及びＲ³²は、それぞれ、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、Ｒ³¹はＲ³²に結合しており、Ｒ³¹がＲ³²に結合した基が酸素原子を有していてもよいヒドロカルビレン基を表す。） Examples of the nitrogen atom-containing group include a substituted amino group. As a substituted amino group, the substituted amino group represented by following formula (3) can be mentioned.

(R ³¹ and R ³² are each a hydrocarbyl group, or, or represents a trihydrocarbylsilyl group, or, R ³¹ is bonded to R ^32, a group R ³¹ is bonded to R ³² is perforated oxygen atom Represents an optionally hydrocarbylene group.)

Examples of the hydrocarbyl group for R ³¹ and R ³² include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl 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. Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group and isopropenyl group. An ethynyl group can be mentioned as an alkynyl group. A phenyl group can be mentioned as an aryl group. A benzyl group can be mentioned as an aralkyl group.

The number of carbon atoms of the hydrocarbyl group of R ³¹ and R ³² is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group for R ³¹ and R ³² is preferably an alkyl group, more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group of R ³¹ and R ³² include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyl-dimethylsilyl group.

The trihydrocarbylsilyl group of R ³¹ and R ³² is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

In the group in which R ³¹ is bonded to R ³² , the hydrocarbylene group optionally having an oxygen atom represents a hydrocarbylene group or a substituted hydrocarbylene group having an oxygen atom as a hetero atom. Examples of the hydrocarbylene group include an alkylene group, and examples of the alkylene group include polymethylene groups such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the substituted hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group in which R ³¹ is bonded to R ³² is preferably 2 to 20, more preferably 3 to 8, and further preferably 4 to 6.

In the group in which R ³¹ is bonded to R ³² , the hydrocarbylene group which may have an oxygen atom is preferably a hydrocarbylene group, more preferably an alkylene group, still more preferably a polymethylene group. is there.

  In the conjugated diene polymer having a nitrogen atom-containing group at at least one polymer chain end, the nitrogen atom-containing group is preferably a substituted amino group, more preferably a substitution represented by the above formula (3). It is an amino group.

More preferably, the nitrogen atom-containing group is a substituted amino group represented by the formula (3),
R ³¹ and R ³² are linear alkyl groups having 1 to 4 carbon atoms, or R ³¹ is bonded to R ³² and R ³¹ is bonded to R ³² is a polymethylene group having 3 to 8 carbon atoms. Is a substituted amino group.

  Particularly preferred as the nitrogen atom-containing group is a dimethylamino group or a diethylamino group.

[Method for producing conjugated diene polymer]
As a preferred production method of the conjugated diene polymer of the present invention, a conjugated diene and a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom by an alkali metal catalyst in a hydrocarbon solvent, Examples thereof include a method of polymerizing a monomer component containing a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom via a hydrocarbylene group.

  The monomer component includes a conjugated diene, a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a substituted amino group that is bonded to a silicon atom via a hydrocarbylene group. In addition to the silicon-containing vinyl monomer, an aromatic vinyl compound is preferably contained. The aromatic vinyl compound is preferably styrene.

  The hydrocarbon solvent is a solvent that does not deactivate the alkali metal catalyst. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, and hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and alicyclic hydrocarbons such as cyclopentane and cyclohexane. I can give you. One or more of these are used.

  Polymerization of the monomer component is an agent for adjusting the vinyl bond amount of the monomer unit derived from the conjugated diene, a compound other than the monomer unit derived from the conjugated diene in the conjugated diene polymer chain and the conjugated diene. May be carried out in the presence of an agent for adjusting the distribution of monomer units derived from (hereinafter collectively referred to as “adjusting agent”). Examples of the adjusting agent include ether compounds, tertiary amines, phosphine compounds, alkali metal alkoxides, and alkali metal phenoxides. Examples of ether compounds include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; aliphatics such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Diethers; aliphatic triethers such as diethylene glycol diethyl ether and diethylene glycol dibutyl ether; and aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, 1,1,2,2-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline, and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. Examples of the alkali metal alkoxide include sodium-tert-butoxide, potassium-tert-butoxide, sodium-tert-pentoxide, and potassium-tert-pentoxide. Examples of the alkali metal phenoxide include sodium phenoxide and potassium phenoxide. One or more of these can be used.

  Of the monomers introduced or supplied to the polymerization reactor, the amount of the silicon-containing vinyl monomer in which the substituted amino group is bonded to the silicon atom, and the substituted amino group is bonded to the silicon atom via the hydrocarbyl group. The total amount of the silicon-containing vinyl monomer is preferably 0.02% by weight in order to improve fuel economy by setting the total amount of monomers charged or supplied to the polymerization reactor to 100% by weight. Or more, more preferably 0.04% by weight or more, and still more preferably 0.2% by weight or more. Moreover, in order to improve grip property, Preferably it is 20 weight% or less, More preferably, it is 7 weight% or less, More preferably, it is 3.5 weight% or less.

  Silicon-containing vinyl system in which the substituted amino group is bonded to the silicon atom in an amount of the silicon-containing vinyl monomer in which the substituted amino group charged or supplied to the polymerization reactor is bonded to the silicon atom via the hydrocarbyl group Weight ratio to the amount of monomer (a silicon-containing vinyl monomer in which the substituted amino group is bonded to the silicon atom via the hydrocarbyl group / a silicon-containing vinyl monomer in which the substituted amino group is bonded to the silicon atom) The body) is preferably 10/90 or more, more preferably 20/80 or more, in order to improve fuel economy and grip. Moreover, Preferably it is 90/10 or less, More preferably, it is 80/20 or less.

  Among the monomers charged or supplied to the polymerization reactor, the amount of conjugated diene is preferably 40% by weight or more, with the total amount of monomers charged or supplied to the polymerization reactor being 100% by weight.

  When the monomer charged or supplied to the polymerization reactor contains an aromatic vinyl compound, the total amount of the conjugated diene and the aromatic vinyl compound among the monomers charged or supplied to the polymerization reactor is the polymerization reactor. The total amount of monomers to be charged or supplied to 100 is 100% by weight, preferably 99.98% by weight or less, more preferably 99.96% by weight or less, and further preferably 99.8% by weight or less. . Further, it is preferably 80% by weight or more, more preferably 93% by weight or more, and further preferably 96.5% by weight or more.

  When the monomer charged or supplied to the polymerization reactor contains an aromatic vinyl compound, the weight ratio of the amount of conjugated diene charged or supplied to the polymerization reactor to the amount of aromatic vinyl compound (conjugated diene / aromatic vinyl) The compound) is preferably 50/50 or more, more preferably 55/45 or more, in order to improve fuel economy. Moreover, in order to improve grip property and tensile strength, Preferably it is 90/10 or less, More preferably, it is 85/15 or less.

  Examples of alkali metal catalysts used for polymerizing monomer components to obtain conjugated diene polymers include organic alkali metal compounds such as organic lithium compounds, organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Can give. Examples of the organic lithium compound include hydrocarbyl lithium compounds and hydrocarbylene dilithium compounds. Examples of the organic sodium compound include sodium naphthalenide and sodium biphenylide. An example of the organic potassium compound is potassium naphthalenide.

  Examples of hydrocarbyl lithium compounds include alkyl lithium compounds such as methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl lithium, and n-decyl lithium. Arylaryl compounds such as phenyllithium, 2-naphthyllithium and 2-butylphenyllithium; arylalkyllithium compounds such as 4-phenylbutyllithium; cycloalkyllithium compounds such as cyclopentyllithium and cyclohexyllithium. The hydrocarbyl lithium compound is preferably an alkyl lithium compound, and more preferably n-butyl lithium or sec-butyl lithium.

  Examples of the hydrocarbylene dilithium compound include 1,4-dilithio-2-butene and 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene.

  The amount of the alkali metal catalyst used for the polymerization of the monomer component is preferably 0.01 mmol to 15 mmol per 100 g of the monomer component used in the polymerization.

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

  The polymerization temperature 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.

When the conjugated diene polymer is a conjugated diene polymer having a nitrogen atom-containing group at at least one polymer chain end (hereinafter also referred to as a nitrogen atom-containing conjugated diene polymer), the conjugated diene polymer Examples of the production method include the following method (a) and method (b).
(A) A monomer component is polymerized by the above-described method, and a modifier having a nitrogen atom-containing group is added to the resulting polymer solution containing the conjugated diene polymer, and the active terminal of the conjugated diene polymer is added. A method of producing a nitrogen atom-containing conjugated diene polymer by reacting the modifier with the modifier.
(B) A method for producing a nitrogen atom-containing conjugated diene polymer by polymerizing a monomer component using an organic alkali metal compound having a nitrogen atom-containing group as an alkali metal catalyst.

  In the method (a), a compound containing a nitrogen atom and a carbonyl group may be mentioned as a preferable modifier having a nitrogen atom-containing group.

（式中、Ｒ⁴¹は水素原子またはメチル基を表し、Ｒ⁴²は水素原子またはメチル基を表し、Ｒ⁴³及びＲ⁴⁴は、それぞれ、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、Ｒ⁴³はＲ⁴⁴に結合しており、Ｒ⁴³がＲ⁴⁴に結合した基が酸素原子を有していてもよいヒドロカルビレン基を表す。ｑは１〜１０の整数を表す。） As the compound containing a nitrogen atom and a carbonyl group, a compound represented by the following formula (4) is preferable.

(Wherein R ⁴¹ represents a hydrogen atom or a methyl group, R ⁴² represents a hydrogen atom or a methyl group, and R ⁴³ and R ⁴⁴ each represents a hydrocarbyl group or a trihydrocarbylsilyl group, or R ⁴³ is bonded to R ⁴⁴ , and R ⁴³ represents a hydrocarbylene group in which the group bonded to R ⁴⁴ may have an oxygen atom, q represents an integer of 1 to 10.)

R ^{41 in the} formula (4) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ^{42 in the} formula (4) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

  Q of Formula (4) represents an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 3.

Examples of the hydrocarbyl group of R ⁴³ and R ⁴⁴ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl 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. Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group and isopropenyl group. An ethynyl group can be mentioned as an alkynyl group. A phenyl group can be mentioned as an aryl group. A benzyl group can be mentioned as an aralkyl group.

The number of carbon atoms of the hydrocarbyl group of R ⁴³ and R ⁴⁴ is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 to 2.

The hydrocarbyl group for R ⁴³ and R ⁴⁴ is preferably an alkyl group, more preferably a linear alkyl group.

The trihydrocarbyl silyl group R ⁴³ and R ^44, a trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tert- butyl - can be given trialkylsilyl group such as a dimethylsilyl group.

The trihydrocarbylsilyl group of R ⁴³ and R ⁴⁴ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

In the group in which R ⁴³ is bonded to R ⁴⁴ , the hydrocarbylene group which may have an oxygen atom represents a hydrocarbylene group or a substituted hydrocarbylene group having an oxygen atom as a hetero atom. Examples of the hydrocarbylene group include an alkylene group, and examples of the alkylene group include polymethylene groups such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the substituted hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group in which R ⁴³ is bonded to R ⁴⁴ is preferably 2 to 20, more preferably 3 to 8, and still more preferably 4 to 6.

In the group in which R ⁴³ is bonded to R ⁴⁴ , the hydrocarbylene group which may have an oxygen atom is preferably a hydrocarbylene group, more preferably an alkylene group, still more preferably a polymethylene group. is there.

Among the compounds represented by the formula (4), examples of the compound in which R ⁴¹ is a hydrogen atom and R ⁴² is a hydrogen atom include the following compounds.

A compound wherein q in formula (4) is 1;
N- (dimethylaminomethyl) acrylamide,
N- (ethylmethylaminomethyl) acrylamide,
N- (diethylaminomethyl) acrylamide,
N- (di-n-propylaminomethyl) acrylamide,
N- (di-n-butylaminomethyl) acrylamide,
N- [bis (trimethylsilyl) aminomethyl] acrylamide N- (1-pyrrolidinylmethyl) acrylamide N- (piperidinomethyl) acrylamide N- (1-hexamethyleneiminomethyl) acrylamide N- (morpholinomethyl) acrylamide.

A compound wherein q in formula (4) is 2;
N- [2- (dimethylamino) ethyl] acrylamide,
N- [2- (ethylmethylamino) ethyl] acrylamide,
N- [2- (diethylamino) ethyl] acrylamide,
N- [2- (di-n-propylamino) ethyl] acrylamide,
N- [2- (di-n-butylamino) ethyl] acrylamide,
N- {2- [bis (trimethylsilyl) amino] ethyl} acrylamide N- [2- (1-pyrrolidinyl) ethyl] acrylamide N- (2-piperidinoethyl) acrylamide N- [2- (1-hexamethyleneimino) ethyl] Acrylamide N- (2-morpholinoethyl) acrylamide.

A compound in which q in formula (4) is 3;
N- [3- (dimethylamino) propyl] acrylamide,
N- [3- (ethylmethylamino) propyl] acrylamide,
N- [3- (diethylamino) propyl] acrylamide,
N- [3- (di-n-propylamino) propyl] acrylamide N- [3- (di-n-butylamino) propyl] acrylamide,
N- {3- [bis (trimethylsilyl) amino] propyl} acrylamide N- [3- (1-pyrrolidinyl) propyl] acrylamide N- (3-piperidinopropyl) acrylamide N- [3- (1-hexamethyleneimino ) Propyl] acrylamide N- (3-morpholinopropyl) acrylamide

A compound wherein q in formula (4) is 4;
N- [4- (dimethylamino) butyl] acrylamide,
N- [4- (ethylmethylamino) butyl] acrylamide,
N- [4- (diethylamino) butylacryl] amide,
N- [4- (di-n-propylamino) butyl] acrylamide,
N- [4- (Di-n-butylamino) butyl] acrylamide N- {4- [bis (trimethylsilyl) amino] butyl} acrylamide N- [4- (1-pyrrolidinyl) butyl] acrylamide N- (4-piperidinobutyl ) Acrylamide N- [4- (1-hexamethyleneimino) butyl] acrylamide N- (4-morpholinobutyl) acrylamide.

Among the compounds represented by the formula (4), examples of the compound in which R ⁴¹ is a methyl group and R ⁴² is a hydrogen atom include the following compounds.

A compound wherein q in formula (4) is 1;
N- (dimethylaminomethyl) methacrylamide,
N- (ethylmethylaminomethyl) methacrylamide,
N- (diethylaminomethyl) methacrylamide,
N- (di-n-propylaminomethyl) methacrylamide,
N- (di-n-butylaminomethyl) methacrylamide,
N- [bis (trimethylsilyl) aminomethyl] methacrylamide N- (1-pyrrolidinylmethyl) methacrylamide N- (piperidinomethyl) methacrylamide N- (1-hexamethyleneiminomethyl) methacrylamide N- (morpholinomethyl) methacryl Amides.

A compound wherein q in formula (4) is 2;
N- [2- (dimethylamino) ethyl] methacrylamide,
N- [2- (ethylmethylamino) ethyl] methacrylamide,
N- [2- (diethylamino) ethyl] methacrylamide,
N- [2- (di-n-propylamino) ethyl] methacrylamide,
N- [2- (di-n-butylamino) ethyl] methacrylamide,
N- {2- [bis (trimethylsilyl) amino] ethyl} methacrylamide N- [2- (1-pyrrolidinyl) ethyl] methacrylamide N- (2-piperidinoethyl) methacrylamide N- [2- (1-hexamethyleneimino ) Ethyl] methacrylamide N- (2-morpholinoethyl) methacrylamide.

A compound in which q in formula (4) is 3;
N- [3- (dimethylamino) propyl] methacrylamide,
N- [3- (ethylmethylamino) propyl] methacrylamide,
N- [3- (diethylamino) propyl] methacrylamide,
N- [3- (di-n-propylamino) propyl] methacrylamide N- [3- (di-n-butylamino) propyl] methacrylamide,
N- {3- [bis (trimethylsilyl) amino] propyl} methacrylamide N- [3- (1-pyrrolidinyl) propyl] methacrylamide N- (3-piperidinopropyl) methacrylamide N- [3- (1- Hexamethyleneimino) propyl] methacrylamide N- (3-morpholinopropyl) methacrylamide

A compound wherein q in formula (4) is 4;
N- [4- (dimethylamino) butyl] methacrylamide,
N- [4- (ethylmethylamino) butyl] methacrylamide,
N- [4- (diethylamino) butyl] methacrylamide,
N- [4- (di-n-propylamino) butyl] methacrylamide,
N- [4- (Di-n-butylamino) butyl] methacrylamide N- {4- [bis (trimethylsilyl) amino] butyl} methacrylamide N- [4- (1-pyrrolidinyl) butyl] methacrylamide N- ( 4-piperidinobutyl) methacrylamide N- [4- (1-hexamethyleneimino) butyl] methacrylamide N- (4-morpholinobutyl) methacrylamide.

In the method (a), the modifier having a nitrogen atom-containing group is preferably a compound represented by the formula (4),
More preferably, it is a compound represented by formula (4), wherein in formula (4), R ⁴¹ is a hydrogen atom or a methyl group, R ⁴² is a hydrogen atom, and R ⁴³ and R ⁴⁴ have 1 carbon atom. Or a group in which R ⁴³ is bonded to R ⁴⁴ , R ⁴³ is bonded to R ⁴⁴ is an alkylene group having 2 to 20 carbon atoms, and q is an integer of 2 to 5 A compound,
More preferably, it is a compound represented by formula (4), wherein in formula (4), R ⁴¹ is a hydrogen atom, R ⁴² is a hydrogen atom, and R ⁴³ and R ⁴⁴ have 1 to 4 carbon atoms. or a straight-chain alkyl group, or R ⁴³ is bonded to R ^44, a group R ⁴³ is bonded to R ⁴⁴ is a polymethylene group having 3 to 8 carbon atoms, a compound q is 3.

The modifier having a nitrogen atom-containing group is particularly preferably
N- [3- (dimethylamino) propyl] acrylamide,
Or N- [3- (diethylamino) propyl] acrylamide,
It is.

  In the above method (a), the addition amount of the modifier having a nitrogen atom-containing group is usually from 0.1 mol to 3 mol, preferably from 0.5 mol to 2 mol, per mol of the alkali metal catalyst used for the polymerization. Yes, and more preferably 0.7 mol to 1.5 mol.

  In the method (a), the temperature at which the conjugated diene polymer and the modifier having a nitrogen atom-containing group are reacted is usually 25 ° C to 100 ° C, preferably 35 ° C to 90 ° C, more preferably. Is 50 ° C to 80 ° C. The reaction time is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour.

（式（５）中、Ｍはアルカリ金属原子を表し、Ｒ⁵¹及びＲ⁵²は、それぞれ、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、Ｒ⁵¹はＲ⁵²に結合しており、Ｒ⁵¹がＲ⁵²に結合した基が酸素原子を有していてもよいヒドロカルビレン基を表し、Ｒ⁵³はヒドロカルビレン基を表し、ｒは０又は１を表す。） In the method (b), as a suitable organic alkali metal compound having a nitrogen atom-containing group, a compound represented by the following formula (5) can be exemplified.

(In the formula (5), M represents an alkali metal atom, R ⁵¹ and R ⁵² each represent a hydrocarbyl group or a trihydrocarbylsilyl group, or R ⁵¹ is bonded to R ⁵² ; R ⁵¹ represents a hydrocarbylene group in which the group bonded to R ⁵² may have an oxygen atom, R ⁵³ represents a hydrocarbylene group, and r represents 0 or 1.)

  In formula (5), M represents an alkali metal atom. Examples of the alkali metal atom include Li, Na, K, Rb, and Cs, preferably Li.

Examples of the hydrocarbyl group of R ⁵¹ and R ⁵² include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl 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. Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group and isopropenyl group. An ethynyl group can be mentioned as an alkynyl group. A phenyl group can be mentioned as an aryl group. A benzyl group can be mentioned as an aralkyl group.

The number of carbon atoms of the hydrocarbyl group of R ⁵¹ and R ⁵² is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 to 2.

The hydrocarbyl group for R ⁵¹ and R ⁵² is preferably an alkyl group, more preferably a linear alkyl group.

The trihydrocarbyl silyl group R ⁵¹ and R ^52, a trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tert- butyl - can be given trialkylsilyl group such as a dimethylsilyl group.

The trihydrocarbylsilyl group of R ⁵¹ and R ⁵² is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

In the group in which R ⁵¹ is bonded to R ⁵² , the hydrocarbylene group which may have an oxygen atom represents a hydrocarbylene group or a substituted hydrocarbylene group having an oxygen atom as a hetero atom. Examples of the hydrocarbylene group include an alkylene group, and examples of the alkylene group include polymethylene groups such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the substituted hydrocarbylene group having an oxygen atom as a hetero atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group in which R ⁵¹ is bonded to R ⁵² is preferably 2 to 20, more preferably 3 to 8, and further preferably 4 to 6.

In the group in which R ⁵¹ is bonded to R ⁵² , the hydrocarbylene group which may have an oxygen atom is preferably a hydrocarbylene group, more preferably an alkylene group, still more preferably a polymethylene group. is there.

In the formula (5), R ⁵³ represents a hydrocarbylene group. Examples of the hydrocarbylene group for R ⁵³ include an alkanediyl group, an alkenediyl group, and an arylene group. Examples of the alkanediyl group include a methylene group; a polymethylene group such as an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group; and a 2,2,4-trimethylhexane-1,6-diyl group. Examples of the alkenediyl group include but-2-ene-1,4-diyl group, 2-methylbut-2-ene-1,4-diyl group and penta-2-ene-1,5-diyl group. . Examples of the arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,3-naphthylene group, and 1,4-naphthylene group.

In addition, examples of the hydrocarbylene group of R ⁵³ include a group in which 1 to 10 structural units derived from a conjugated diene are bonded to an alkanediyl group. For example, a group in which 1 to 10 structural units derived from isoprene are bonded to a methylene group, a group in which 1 to 10 structural units derived from isoprene are bonded to an ethylene group, and 1 to 10 units of structural units derived from isoprene. And a group in which is bonded to a trimethylene group. In the group in which 1 to 10 structural units derived from the conjugated diene are bonded to the alkanediyl group, the conjugated diene is preferably isoprene and / or butadiene, and the number of structural units derived from the conjugated diene is: Preferably, it is 1 unit to 5 units, and the alkanediyl group is preferably a methylene group or a polymethylene group, and the number of carbon atoms of the alkanediyl group is preferably 1-6, more preferably 2-4. Yes, more preferably 2 or 3.

The hydrocarbylene group for R ⁵³ is preferably a group in which 1 to 10 structural units derived from a conjugated diene are bonded to an alkanediyl group, or an alkanediyl group, more preferably from butadiene and / or isoprene. It is a group in which 1 to 10 structural units derived from a conjugated diene are bonded to a methylene group or a polymethylene group, or a polymethylene group, and more preferably 1 to 10 structural units derived from isoprene. It is a group bonded to 2 to 4 polymethylene groups, particularly preferably a group in which 1 to 5 structural units derived from isoprene are bonded to an ethylene group or a trimethylene group.

  In the formula (5), r represents 0 or 1, preferably 1.

Among the compounds represented by the formula (5), compounds in which r is 1 and R ⁵¹ and R ⁵² are hydrocarbyl groups include 2- (dimethylamino) ethyllithium, 2- (diethylamino) ethyllithium, 3 Examples thereof include dialkylaminoalkyllithium such as-(dimethylamino) propyllithium and 3- (diethylamino) propyllithium. Moreover, the compound which made 1 mol-10 mol conjugated dienes react with the said dialkylaminoalkyl lithium per 1 mol of the said compound can also be mention | raise | lifted.

Among the compounds represented by the formula (5), r is 1, and R ⁵¹ and R ⁵² are bonded to form a hydrocarbylene group, such as 3- (1-pyrrolidinyl) propyllithium, 3-pi Examples thereof include cyclic aminoalkyllithiums such as peridinopropyllithium and 3- (1-hexamethyleneimino) propyllithium. Moreover, the compound which made 1 mol-10 mol conjugated dienes react with the said cyclic aminoalkyl lithium per 1 mol of the said compounds can also be mention | raise | lifted.

Of the compounds represented by the formula (5), r is 1, R ⁵¹ is bonded to R ^52, a group R ⁵¹ is bonded to R ⁵² is a substituted hydrocarbylene group having an oxygen atom as a hetero atom An example of the compound is 3- (4-morpholino) propyl lithium. Moreover, the compound which made 1 mol-10 mol conjugated dienes react with the said compound per 1 mol of the said compounds can also be mention | raise | lifted.

The compound represented by the formula (5) is preferably such that r is 1, and R ⁵³ is a structural unit derived from at least one conjugated diene selected from the group consisting of butadiene and isoprene. A group bonded to a polymethylene group having 2 to 6 carbon atoms (provided that the methylene group or the polymethylene group is bonded to the nitrogen atom of the formula (5)), or a polymethylene group having 2 to 6 carbon atoms; Compound in which ⁵¹ and R ⁵² are alkyl groups having 1 to 10 carbon atoms, or R ⁵¹ is bonded to R ⁵² and R ⁵¹ is bonded to R ⁵² is an alkylene group having 2 to 20 carbon atoms And
More preferably, r is 1, and R ⁵³ is a group in which 1 to 10 structural units derived from isoprene are bonded to a polymethylene group having 2 to 4 carbon atoms (wherein the polymethylene group is represented by formula (5) R ⁵¹ and R ⁵² are linear alkyl groups having 1 to 4 carbon atoms, or R ⁵¹ is bonded to R ⁵² and R ⁵¹ is bonded to R ^52. Is a compound of a polymethylene group having 3 to 8 carbon atoms,
More preferably, r is 1 and R ⁵³ is a group in which 1 to 5 structural units derived from isoprene are bonded to an ethylene group or trimethylene group (wherein the ethylene group or trimethylene group is a nitrogen atom of the formula (5)) And R ⁵¹ and R ⁵² are straight-chain alkyl groups having 1 to 4 carbon atoms.

Particularly preferably, the compound represented by the formula (5) is:
2- (dimethylamino) ethyllithium,
2- (diethylamino) ethyllithium,
3- (dimethylamino) propyllithium,
A compound selected from the group consisting of 3- (diethylamino) propyllithium is a compound obtained by reacting 1 mol to 5 mol of isoprene per 1 mol of the compound.

  The compound represented by the formula (5) may be prepared in a solution containing a monomer component.

  In the method (b), the amount of the organic alkali metal compound having a nitrogen atom-containing group used for the polymerization of the monomer component is preferably 0.01 mmol per 100 g of the monomer component used in the polymerization. ~ 15 mmol.

  In the method (b), another alkali metal catalyst such as n-butyllithium may be used in combination as necessary.

<Coupling>
In the method for producing a conjugated diene polymer of the present invention, a coupling agent may be added to the polymerization solution from the start of polymerization of the monomer to the recovery of the polymer described later. As a coupling agent, the compound represented by following formula (6) can be mentioned. R ⁶¹ _a ML _4-a (6)
Wherein R ⁶¹ 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 (6), silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, tetramethoxysilane, methyltrimethoxysilane, Examples include dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.

  When a coupling agent is added to the polymerization solution, the amount of coupling agent added is preferably 0.03 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. More preferably, it is 0.05 mol or more. 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.

<Recovery of polymer>
In the production method of the present invention, before the polymer is recovered from the solution in which the polymer is dissolved, the unreacted active terminal of the polymer may be treated with an alcohol such as methanol, isopropyl alcohol, or 1-butanol. Good.

  As a method for recovering the conjugated diene polymer from the solution in which the polymer is dissolved, a known method can be used. For example, (A) a method of adding a coagulant to a solution containing the conjugated diene polymer, (B) A method of adding steam to a solution containing a conjugated diene polymer can be mentioned. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

[Polymer composition]
The polymer composition may be prepared by blending the conjugated diene polymer of the present invention with other polymer components or 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 content of the conjugated diene polymer of the present invention in the polymer composition is increased in order to improve fuel economy. The total amount of polymer components (including the conjugated diene polymer) is 100% by weight, preferably 10% by weight or more, and more preferably 20% by 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 materials 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 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 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and thiazole vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram disulfide Thiuram vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N-oxymethylene-2-benzothiazole sulfenamide, N- Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide, N, N′-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine, etc. It can be mentioned guanidine vulcanization accelerators. 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 reinforcing material include silica, calcium silicate, aluminum silicate, and carbon black.

Examples of the silica include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, and precipitated silica. 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 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.

The content of the reinforcing material in the polymer composition is preferably 10 parts by weight or more, more preferably 20 parts by weight with respect to 100 parts by weight of the conjugated diene polymer of the present invention, in order to increase wear resistance and strength. It is at least 30 parts by weight, more preferably at least 30 parts by weight. Moreover, in order to improve reinforcement property, Preferably it is 150 weight part or less, More preferably, it is 120 weight part or less, More preferably, it is 100 weight part or less.

The reinforcing material preferably contains silica in order to improve fuel economy. The content of silica is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, with the total amount of the reinforcing material being 100 parts by weight.

  The reinforcing material preferably contains carbon black in addition to silica. The weight ratio of silica content to carbon black content in the reinforcing material (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.

  As silane coupling agents, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-amino Propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) ) Propi ) 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.

  The amount of the silane coupling agent is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and further preferably 5 to 10 parts by weight with respect to 100 parts by weight of silica. Parts by weight.

  As the extending oil, 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.

  Examples of a method for producing a conjugated diene polymer composition by blending other polymer components and additives with the conjugated diene polymer of the present invention include, for example, known mixing such as roll and Banbury. A method of kneading with a machine 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 ° C to 200 ° C, preferably 140 ° C to 180 ° C.

  The conjugated diene polymer composition of the present invention is excellent in fuel economy and 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 in the vicinity of 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). 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 a strain of 1% and a frequency of 10 Hz. The smaller this value, the better the fuel economy.

5. 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.

Example 1
The inside of the stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas in the polymerization reactor was 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 4.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act on the deactivation of the alkali metal catalyst in advance.

  2.72 g of bis (diethylamino) methylvinylsilane and 2.29 g of dimethyl (piperidinomethyl) vinylsilane were charged into the polymerization reactor. Next, an n-butyllithium n-hexane solution (content of n-butyllithium 12.7 mmol) was charged as an alkali metal catalyst into the polymerization reactor to initiate the polymerization reaction. 1,3-butadiene, styrene, bis (diethylamino) methylvinylsilane while stirring rate is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. And dimethyl (piperidinomethyl) vinylsilane were copolymerized 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, and the charged amount of dimethylpiperidinomethylvinylsilane was 0.11% 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 pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added. Next, the polymerization solution was allowed to stand at room temperature for 24 hours, and the solvent 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 the stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas inside the polymerization reactor was 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 4.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act on the deactivation of the alkali metal catalyst agent in advance.

  2.74 g of bis (diethylamino) methylvinylsilane and 2.35 g of dimethyl (piperidinomethyl) vinylsilane were charged into the polymerization reactor. Next, an n-butyllithium n-hexane solution (content of n-butyllithium 12.8 mmol) was charged as an alkali metal catalyst into the polymerization reactor to initiate the polymerization reaction. 1,3-butadiene, styrene, bis (diethylamino) methylvinylsilane while stirring rate is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. And dimethyl (piperidinomethyl) vinylsilane were copolymerized 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, and the charged amount of dimethyl (piperidinomethyl) vinylsilane was 0.12% by weight.

  Next, while maintaining the polymerization reactor temperature at 65 ° C., the obtained polymerization solution was stirred in the polymerization reactor at a stirring speed of 130 rpm to polymerize 12.8 mmol of N- [3- (dimethylamino) propyl] acrylamide. Added to the 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: 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 3
The inside of the stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas inside the polymerization reactor was 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 4.6 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act on the deactivation of the alkali metal catalyst in advance.

2.74 g of bis (diethylamino) methylvinylsilane and 2.35 g of dimethylpiperidinomethylvinylsilane were charged into the polymerization reactor. Next, a compound obtained by reacting 3- (dimethylamino) propyllithium with isoprene as an alkali metal catalyst [reaction ratio: isoprene / 3- (dimethylamino) propyllithium = 2/1 (molar ratio), manufactured by FMC, Product name: AI-200CE2 (cyclohexane solution)] 14.6 mmol as a cyclohexane solution was charged into the polymerization reactor to initiate the polymerization reaction. 1,3-butadiene, styrene, bis (diethylamino) methylvinylsilane while stirring rate is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. And dimethylpiperidinomethylvinylsilane were copolymerized 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, and the charged amount of dimethylpiperidinomethylvinylsilane was 0.12% by weight. .

  Next, while maintaining the polymerization reactor temperature at 65 ° C., the obtained polymerization solution was stirred in the polymerization reactor at a stirring speed of 130 rpm to polymerize 14.6 mmol of N- [3- (dimethylamino) propyl] acrylamide. Added to the 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: 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.

Comparative Example 1
The inside of a stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas inside the polymerization reactor was 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 hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act on the deactivation of the alkali metal catalyst in advance.

  2.63 g of bis (diethylamino) methylvinylsilane was charged into the polymerization reactor, and then an n-hexane solution of n-butyllithium (content of n-butyllithium 12.3 mmol) was charged into the polymerization reactor. The polymerization reaction was started.

  The polymerization reaction was carried out for 3 hours. During the polymerization reaction, the temperature in the polymerization reactor is adjusted to 65 ° C., the solution in the polymerization reactor is stirred at a stirring speed of 130 rpm, and 912 g of 1,3-butadiene and 288 g of styrene are continuously added in the polymerization reactor. Supplied. The total amount of monomers charged or supplied to the polymerization reactor was 100% by weight, and the amount of bis (diethylamino) methylvinylsilane added was 0.13% by weight.

  20 ml of hexane solution containing 0.8 ml of methanol was put into the polymerization reactor, and the polymerization solution was stirred for 5 minutes.

  2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8.0 g, pentaerythrityl tetrakis 4.0 g of (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was charged into the polymerization reactor, and then the polymerization solution was evaporated at room temperature for 24 hours. Furthermore, it dried under reduced pressure at 55 degreeC for 12 hours, and obtained the polymer. 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.

Comparative Example 2
The inside of a stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed and dried, and the gas inside the polymerization reactor was 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 4.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, a small amount of n-butyllithium hexane solution was introduced into the polymerization reactor as a scavenger in order to detoxify impurities that act on the deactivation of the alkali metal catalyst in advance.

  Then, 2.33 g of dimethyl (piperidinomethyl) vinylsilane was charged into the polymerization reactor, and then an n-hexane solution of n-butyllithium (content of n-butyllithium 12.7 mmol) was charged into the polymerization reactor. The polymerization reaction was started.

  The polymerization reaction was carried out for 3 hours. During the polymerization reaction, the temperature in the polymerization reactor is adjusted to 65 ° C., the solution in the polymerization reactor is stirred at a stirring speed of 130 rpm, and 912 g of 1,3-butadiene and 288 g of styrene are continuously added in the polymerization reactor. Supplied. The total amount of monomers charged or supplied to the polymerization reactor was 100% by weight, and the amount of dimethyl (piperidinomethyl) vinylsilane charged was 0.12% by weight.

  20 ml of hexane solution containing 0.8 ml of methanol was put into the polymerization reactor, and the polymerization solution was stirred for 5 minutes.

  2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8.0 g, pentaerythrityl tetrakis 4.0 g of (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was charged into the polymerization reactor, and then the polymerization solution was evaporated at room temperature for 24 hours. Furthermore, it dried under reduced pressure at 55 degreeC for 12 hours, and obtained the polymer. 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 (5)

  A monomer unit derived from a conjugated diene, a monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, and a substituted amino group via a hydrocarbylene group A conjugated diene polymer having a monomer unit derived from a silicon-containing vinyl monomer bonded to an atom.   The conjugated diene polymer according to claim 1, which has a nitrogen atom-containing group at at least one polymer chain end.   A monomer unit derived from a silicon-containing vinyl monomer in which a substituted amino group is bonded to a silicon atom, with the total amount of monomer units contained in the conjugated diene polymer being 100% by weight, and a substituted amino group The total content of the monomer unit derived from a silicon-containing vinyl monomer bonded to a silicon atom via a hydrocarbyl group is 0.02 wt% or more and 20 wt% or less. 2. The conjugated diene polymer according to 2.   The conjugated diene polymer according to any one of claims 1 to 3 and a reinforcing material, wherein the content of the reinforcing material is 10 parts by weight or more and 150 parts by weight with respect to 100 parts by weight of the conjugated diene polymer. A polymer composition which is:   In hydrocarbon solvent, conjugated diene, silicon-containing vinyl monomer in which substituted amino group is bonded to silicon atom, and substituted amino group bonded to silicon atom through hydrocarbylene group by alkali metal catalyst A method for producing a conjugated diene polymer comprising polymerizing a monomer component containing a silicon-containing vinyl monomer.