WO2018181720A1

WO2018181720A1 - Conjugated diene-based polymer composition and method for producing conjugated diene-based polymer composition

Info

Publication number: WO2018181720A1
Application number: PCT/JP2018/013262
Authority: WO
Inventors: 俊宏信岡; 慶太大野
Original assignee: 住友化学株式会社
Priority date: 2017-03-31
Filing date: 2018-03-29
Publication date: 2018-10-04
Also published as: JPWO2018181720A1; JP7236993B2

Abstract

The conjugated diene-based polymer composition according to the present invention comprises a conjugated diene-based polymer having a weight average molecular weight of 80,000 or larger, and a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group.

Description

Conjugated diene polymer composition and method for producing conjugated diene polymer composition

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

As a polymer composition for an automobile tire, a composition containing a conjugated diene polymer such as a conjugated diene elastomer, polybutadiene, or a styrene-butadiene copolymer is used. When such a polymer composition is stored, a phenomenon called “cold flow” in which the shape of the polymer composition collapses with time may occur. For example, Patent Document 1 discusses reducing cold flow by using a specific elastomer composition.

JP-A-11-209524

A polymer composition using a conjugated diene polymer is required to further improve cold flow. Then, an object of this invention is to provide the manufacturing method of the conjugated diene type polymer composition which can fully suppress a cold flow, and this conjugated diene type polymer composition.

The present invention relates to a conjugated diene polymer composition comprising a conjugated diene polymer having a weight average molecular weight of 80000 or more and a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group.

The present invention also includes a step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene polymer, a conjugated diene polymer, a carbonyl group, and a hydrogen bond with the carbonyl group. And a step of mixing a compound having a functional group that can be formed.

The present invention further includes a step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene polymer, and a compound having a hetero atom and / or a silicon atom. And a step of obtaining a terminal-modified conjugated diene polymer, a terminal-modified conjugated diene polymer, and a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group. The manufacturing method of a conjugated diene type polymer composition provided with the process to mix.

According to the present invention, it is possible to provide a conjugated diene polymer composition capable of sufficiently suppressing cold flow and a method for producing the conjugated diene polymer composition.

This embodiment will be described in detail. In addition, this invention is not limited to the following embodiment.

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. The amino group having a substituent (hereinafter sometimes referred to as a substituted amino group) has a structure in which at least one hydrogen atom of the amino group is replaced with a monovalent atom other than a hydrogen atom or a monovalent group. Or a group having a structure in which two hydrogen atoms of an amino group are replaced with a divalent group. 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 hydrocarbylene group having a nitrogen atom and / or an oxygen atom is a carbon atom and / or a hydrogen atom other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed has a nitrogen atom and / or an oxygen atom. A divalent group having a structure replaced with a group is represented.

[Conjugated Diene Polymer Composition]
The conjugated diene polymer composition of this embodiment includes a conjugated diene polymer having a weight average molecular weight of 80,000 or more, and a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group.

(Compounds having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group)
The compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group according to the present embodiment is an agent that suppresses cold flow of the conjugated diene polymer composition (hereinafter referred to as “cold flow inhibitor” in some cases). .).

The functional group capable of forming a hydrogen bond with the carbonyl group is preferably a group having an oxygen atom or a nitrogen atom. Examples of such a functional group include a group represented by —OH or —NH—. Examples of —OH include alcoholic hydroxyl groups. —NH— may be a group constituting an amino group or a group constituting an amide group. Examples of the compound include an aliphatic hydroxycarboxylic acid compound and an aliphatic amide compound having two or more amide groups (hereinafter sometimes referred to as “aliphatic amide compound”).

The aliphatic hydroxycarboxylic acid compound according to this embodiment is an aliphatic compound having a hydroxyl group and a carboxyl group. The aliphatic hydroxycarboxylic acid compound preferably has a linear hydrocarbon group, and the hydrocarbon group may have an unsaturated bond. When it has an unsaturated bond, a trans isomer is preferable. The number of carbon atoms of the aliphatic hydroxycarboxylic acid compound is preferably 2 to 40, more preferably 6 to 30, and still more preferably 8 to 20.

Examples of the aliphatic hydroxycarboxylic acid compound include hydroxycaprylic acid, hydroxylauric acid, hydroxypalmitic acid, hydroxystearic acid, dihydroxystearic acid and hydroxyelaidic acid. Since the cold flow can be further suppressed, the aliphatic hydroxycarboxylic acid compound is preferably 12-hydroxystearic acid or 2-hydroxycaprylic acid, more preferably 12-hydroxystearic acid.

The aliphatic amide compound may be linear or branched, but is preferably branched because cold flow can be further suppressed. The aliphatic amide compound preferably has 3 or more amide groups, preferably 8 or less, more preferably 6 or less. The aliphatic amide compound preferably has 2 to 8 amide groups, more preferably 3 to 6. The aliphatic amide compound has preferably 11 to 70 carbon atoms, more preferably 17 to 53 carbon atoms. However, the aliphatic amide compound according to this embodiment does not include aliphatic polyamides such as nylon-6.

Examples of the aliphatic amide compound include N-hexanoylglutamic acid diisopropylamide, N-hexanoylglutamic acid dibutylamide, N-hexanoylglutamic acid di-sec-butylamide, N-hexanoylglutamic acid diisobutyramide, N-octanoylglutamic acid diisopropylamide. N-octanoylglutamic acid dibutylamide, N-octanoylglutamic acid di-sec-butyramide, N-octanoylglutamic acid diisobutyramide, N-2-ethylhexanoylglutamic acid dimethylamide, N-2-ethylhexanoylglutamic acid diethylamide, N -2-Ethylhexanoylglutamic acid dipropylamide, N-2-ethylhexanoylglutamic acid diisopropylamide, N-2-ethyl Xanoylglutamic acid dibutylamide, N-2-ethylhexanoylglutamic acid di-sec-butylamide, N-2-ethylhexanoylglutamic acid diisobutyramide, N-2-ethylhexanoylglutamic acid dipentylamide, N-2-ethylhexanoylglutamic acid Dihexylamide, N-decanoylglutamic acid diisopropylamide, N-decanoylglutamic acid dibutylamide, N-decanoylglutamic acid di-sec-butylamide, N-decanoylglutamic acid diisobutyramide, N-lauroylglutamic acid dimethylamide, N-lauroylglutamic acid diethylamide N-lauroyl glutamic acid dipropylamide, N-lauroyl glutamic acid diisopropylamide, N-lauroyl glutamic acid dipropylamide Tyramide, N-lauroylglutamic acid di-sec-butylamide, N-lauroylglutamic acid diisobutylamide, N-lauroylglutamic acid dipentylamide, N-lauroylglutamic acid dihexylamide, N-lauroylglutamic acid distearylamide, N-palmitoylglutamic acid diisopropylamide, N- Palmitoylglutamic acid dibutylamide, N-palmitoylglutamic acid di-sec-butylamide, N-palmitoylglutamic acid diisobutyramide, N-myristoylglutamic acid diisopropylamide, N-myristoylglutamic acid dibutylamide, N-myristoylglutamic acid di-sec-butylamide, N-myristoylglutamic acid Diisobutyramide, N-2-ethylhexanoyl ass N-ethylhexanoyl aspartic acid dibutylamide, N-2-ethylhexanoyl aspartic acid di-secamide, N-2-ethylhexanoyl aspartic acid diisobutyramide, N-lauroyl aspartate diisopropylamide Amides, N-lauroyl aspartic acid dibutylamide, N-lauroyl aspartic acid di-sec-butyramide, N-lauroyl aspartic acid diisobutyramide, dicaproyl lysine lauryl amide, dicaproyl lysine lauryl ester and lauroyl phenylalanine lauryl amide . The aliphatic amide compound is preferably N-lauroyl-L-glutamic acid-α, γ-dibutyramide.

The content of the compound is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the conjugated diene polymer because cold flow can be further suppressed. More preferably, it is 0.3 to 2 parts by mass.

(Conjugated diene polymer)
The weight average molecular weight (Mw) of the conjugated diene polymer according to the present embodiment is 80000 or more in order to increase the tensile strength at break, preferably 80000 to 1200000, more preferably 85000 to 800000, More preferably, it is 85,000 to 500,000. When the weight average molecular weight (Mw) of the conjugated diene polymer is less than 80000, it becomes a liquid polymer and is difficult to use as a rubber component for automobile tires. The molecular weight distribution of the conjugated diene polymer is preferably 1 to 5 and more preferably 1 to 2 in order to improve fuel economy. The molecular weight distribution is obtained by measuring the number average molecular weight (Mn) and Mw by gel permeation chromatography (GPC) method and dividing Mw by Mn. Mw and Mn can be measured by, for example, a GPC apparatus “HLC-8020” manufactured by Tosoh Corporation. As the column, for example, “GMH-XL” manufactured by Tosoh Corporation can be used. As the molecular weight standard substance, for example, standard polystyrene manufactured by Tosoh Corporation can be used.

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

The vinyl bond content of the conjugated diene polymer is preferably 80 mol% or less, more preferably 70 mol%, in order to improve fuel economy, with the content of monomer units derived from the conjugated diene compound being 100 mol%. It is as follows. Further, the vinyl bond amount of the conjugated diene polymer is preferably 10 mol% or more, more preferably 15 mol, with the content of the monomer unit derived from the conjugated diene compound being 100 mol% in order to enhance grip properties. % Or more, more preferably 20 mol% or more, and particularly preferably 30 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 can be produced by polymerizing a monomer containing a conjugated diene compound using a polymerization initiator. Hereinafter, each component which can be used for preparation of the conjugated diene polymer according to the present embodiment will be described.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1, and the like. Examples include 3-butadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and 1,3-hexadiene, and 1,3-butadiene or isoprene is preferable. These conjugated diene compounds may be used alone or in combination of two or more.

The monomer according to this embodiment can contain an aromatic vinyl compound together with a conjugated diene compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene, and styrene is preferable.

The content of the aromatic vinyl compound in the monomer is preferably 5% by mass or more, more preferably 10% by mass or more, with the total amount of monomers being 100% by mass. Further, the content of the aromatic vinyl compound is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less in order to improve fuel economy.

The conjugated diene polymer according to the present embodiment may have other monomer units other than the conjugated diene monomer unit, the modifier monomer unit, and the aromatic vinyl monomer unit. . Other monomers include chain olefin compounds such as ethylene, propylene and 1-butene; cyclic olefin compounds such as cyclopentene and 2-norbornene; 1,5-hexadiene, 1,6-heptadiene and 1,7-octadiene And non-conjugated diene compounds such as dicyclopentadiene and 5-ethylidene-2-norbornene. The content ratio of the other monomer units in the conjugated diene polymer chain according to the present embodiment is preferably 10% by mass or less, more preferably 5% by mass or less.

The conjugated diene polymer according to the present embodiment includes a polymer block (A) having an isoprene monomer unit as a main component and a polymer block (B) having a 1,3-butadiene monomer unit as a main component. And may be provided.

The Mw of the polymer block (A) is preferably 1000 to 30000. The polymer block (A) is not particularly limited as long as the main component is an isoprene monomer unit, and may be composed of only an isoprene monomer unit or isoprene monomer. It may be composed of a unit and a monomer monomer unit other than isoprene. As a monomer other than isoprene, an aromatic vinyl compound may be used. The polymer block (A) may contain an isoprene monomer unit and an aromatic vinyl monomer unit.

The content ratio of the isoprene monomer unit in the polymer block (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. Moreover, the upper limit of the content rate of an isoprene monomer unit is although it does not specifically limit, Preferably it is 99 mass% or less. By setting the content ratio of the isoprene monomer unit in the polymer block (A) within the above range, when a reinforcing material such as silica is blended with the conjugated diene polymer, the conjugated diene polymer and silica, etc. The affinity with the reinforcing material can be further increased, and the resulting rubber cross-linked product can be made more excellent in low heat buildup and wet grip properties.

Examples of the polymerization initiator include alkali metals, complexes of alkali metals and polar compounds, oligomers having alkali metals, organic alkali metal compounds, Ziegler-Natta catalysts, and metallocene catalysts. As the polymerization initiator, an organic alkali metal compound is preferable. The polymerization initiators may be used alone or in combination of two or more.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the complex of an alkali metal and a polar compound include a potassium-tetrahydrofuran complex and a potassium-diethoxyethane complex. Examples of the oligomer having an alkali metal include sodium salt of α-methylstyrene tetramer.
Examples of the organic alkali metal compound include an organic alkali metal compound having a group containing a nitrogen atom and an organic alkali metal compound having a hydrocarbyl group.

Examples of the organic alkali metal compound having a hydrocarbyl group include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl lithium, n-decyl lithium, and phenyl. Lithium, n-propyllithium, isopropyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclopentyllithium, 1,4-dilithiobutane, 1,4-dilithio-2-butene, 1 , 3,5-trilithiobenzene, 1,3,5-tris (lithiomethyl) benzene, 2,3,5-tris (lithiomethyl) naphthalene, 1,4,5-tris (lithiomethyl) naphthalene, 1,3,3 - Ririchiookuchin, sodium naphthalenide, sodium biphenylide and potassium naphthalenide and the like, preferably a n- butyl lithium.

Examples of the organic alkali metal compound having a group containing a nitrogen atom include methylaminopropyllithium, diethylaminopropyllithium, tert-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide, lithium pyrrolidide, Examples thereof include compounds obtained by reacting isoprene with lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, 3- (dimethylamino) propyllithium or 3- (diethylamino) propyllithium.

The organic alkali metal compound having a group containing a nitrogen atom is preferably an organic alkali metal compound having a group represented by the following formula (2).

In the formula (2), R ²¹ and R ²² each independently represents a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or a part of R ²¹ and one of R ²² A hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom formed by bonding with a moiety, represented by —Si (R ³² ) ₂ — (CH ₂ ) _x —Si (R ³² ) ₂ — A group having 5 to 20 carbon atoms (R ³² represents a hydrocarbyl group, x is an integer of 1 to 10), or —Si (R ³³ ) ₂ — (CH ₂ ) _y — A group having 4 to 20 carbon atoms (R ³³ represents a hydrocarbyl group, and y is an integer of 2 to 11) may be formed.

Examples of the hydrocarbyl group in R ²¹ and R ²² 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, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, and n-octyl group. , N-dodecyl group, cyclopentyl group and cyclohexyl group. Examples of the alkenyl group include a vinyl group, an aryl group, a 1-propenyl group, and an isopropenyl group. Examples of the alkynyl group include ethynyl group and 2-propynyl group. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group. The hydrocarbyl group is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the hydrocarbyl group having a substituent in R ²¹ and R ²² include a hydrocarbyl group in which one or more hydrogen atoms are substituted with a substituted amino group, a hydrocarbyl group in which one or more hydrogen atoms are substituted with a hydrocarbyloxy group, Examples thereof include a hydrocarbyl group in which the above hydrogen atoms are substituted with a trialkylsilyl group, a hydrocarbyl group in which one or more hydrogen atoms are substituted with a trialkoxysilyl group, and the like.

Here, examples of the substituted amino group include N, N-dimethylamino group, N, N-diethylamino group and other N, N-dialkylamino groups, 1-pyrrolyl group, 1-piperidyl group, 1-imidazolyl group and the like. Of the cyclic amino group.

Examples of the hydrocarbyl group in which one or more hydrogen atoms are substituted with a substituted amino group include, for example, N, N-dimethylaminomethyl group, 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ) (N, N-dialkylamino) alkyl groups such as ethyl group, 3- (N, N-dimethylamino) propyl group, 3- (N, N-diethylamino) propyl group; 4- (N, N-dimethylamino) (N, N-dialkylamino) such as phenyl group, 3- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 3- (N, N-diethylamino) phenyl group Aryl group; (N, N-dialkylamino) alkyl such as 4- (N, N-dimethylamino) methylphenyl group and 4- [2- (N, N-dimethylamino) ethyl] phenyl group An aryl group; an alkyl group substituted with a cyclic amino group such as 3- (1-pyrrolidinyl) propyl group, 3- (1-piperidinyl) propyl group, 3- (1-imidazolyl) propyl group; 4- (1-pyrrolidinyl) An aryl group substituted with a cyclic amino group such as a phenyl group, 4- (1-piperidinyl) phenyl group, 4- (1-imidazolyl) phenyl group; 4- [2- (1-pyrrolidinyl) ethyl] phenyl group; An alkylaryl group substituted with a cyclic amino group such as 4- [2- (1-piperidinyl) ethyl] phenyl group and 4- [2- (1-imidazolyl) ethyl] phenyl group can be exemplified.

Examples of the hydrocarbyl group in which one or more hydrogen atoms are substituted with a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.
Examples of the hydrocarbyl group in which one or more hydrogen atoms are substituted with a trialkylsilyl group include trialkylsilylalkyl groups such as trimethylsilylmethyl group, 2-trimethylsilylethyl group, and 3-trimethylsilylpropyl group.
Examples of the hydrocarbyl group in which one or more hydrogen atoms are substituted with trialkoxysilyl groups include trialkoxysilylalkyl groups such as trimethoxysilylmethyl group, 2-trimethoxysilylethyl group, and 3-trimethoxysilylpropyl group. Can be mentioned.

The hydrocarbyl group which may have a substituent is preferably a hydrocarbyl group which may have a substituent having 1 to 20 carbon atoms, more preferably a hydrocarbyl group having 1 to 20 carbon atoms, An alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group is more preferable. A group or an ethyl group is particularly preferred.

Examples of the trihydrocarbylsilyl group in R ²¹ and R ²² include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, tert-butyl- A trialkylsilyl group such as a dimethylsilyl group can be mentioned, and a trimethylsilyl group or a triethylsilyl group is preferable.

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom formed by bonding a part of R ^{21 and} a part of R ²² is a hydrocarbylene group or a nitrogen atom and / or It is a hydrocarbylene group having an oxygen atom.

Examples of the hydrocarbylene group include an alkylene group, an alkenediyl group, an arylene group, a group in which an arylene group is bonded to an alkylene group (hereinafter sometimes referred to as an arylene-alkylene group), and the like. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and 2,2,4-trimethylhexane-1,6- A diyl group can be mentioned. Examples of the alkenediyl group include a pentane-2-ene-1,5-diyl group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the arylene-alkylene group include a phenylene-alkylene group, a naphthylene-alkylene group, and a biphenylene-alkylene group. The hydrocarbylene group is preferably an alkylene group, more preferably an alkylene group having 4 to 7 carbon atoms.

Examples of the hydrocarbylene group having a nitrogen atom and / or an oxygen atom include a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, A group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — and the like can be mentioned, and preferably —CH═N—CH ₂ —CH ₂ — or —CH ₂ —CH ₂ — It is a group represented by O—CH ₂ —CH ₂ —.
As the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom, a hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom having 3 to 20 carbon atoms is preferable, A hydrocarbylene group having 3 to 20 carbon atoms is preferable, an alkylene group having 4 to 7 carbon atoms is more preferable, and a tetramethylene group, a pentamethylene group, or a hexamethylene group is still more preferable.

5 to 20 carbon atoms represented by —Si (R ³⁵ ) ₂ — (CH ₂ ) _x —Si (R ³⁵ ) ₂ — formed by bonding a part of R ^{21 and} a part of R ²² The group (R ³⁵ represents a hydrocarbyl group, x represents an integer of 1 or more and 10 or less) is represented by —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —Si (CH ₃ ) ₂ —. Groups and the like.
A group having 4 or more and 20 or less carbon atoms represented by —Si (R ³⁶ ) ₂ — (CH ₂ ) _y — (R ³⁶ is a hydrocarbyl group) formed by bonding a part of R ^{21 and} a part of R ²² And y represents an integer of 2 to 11, and examples thereof include a group represented by —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —CH ₂ —.

R ²¹ and R ²² each independently represents a hydrocarbyl group, or preferably represents a hydrocarbylene group formed by bonding a part of R ^{21 and} a part of R ^22. More preferably an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 4 to 7 carbon atoms formed by bonding a part of R ^{21 and} a part of R ^22. Preferably, each independently represents an alkyl group having 1 to 4 carbon atoms, and more preferably each independently represents a methyl group or an ethyl group.

Specific examples of the organic alkali metal compound having a group represented by the formula (2) include dimethylaminopropyllithium, diethylaminopropyllithium, tert-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide. , Lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide and the like.

As a manufacturing method of the organic alkali metal compound having a group represented by the formula (2), a method using a compound represented by the formula (3), an organic alkali metal compound and a group represented by the formula (2) Examples thereof include a method of reacting with a secondary amine compound.

In formula (3), R ²¹ and R ²² are respectively synonymous with R ²¹ and R ²² in formula (2), R ³¹ represents a hydrocarbylene group having 6 to 100 carbon atoms, and M is Represents an alkali metal atom.

The hydrocarbylene group having 6 to 100 carbon atoms of R ³¹ is preferably a hydrocarbylene group having 7 to 90 carbon atoms, more preferably a hydrocarbylene group having 8 to 80 carbon atoms. is there.

The hydrocarbylene group having 8 to 80 carbon atoms of R ³¹ is preferably a group represented by the formula (3-1).

In formula (3-1), R ³⁴ represents a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and i and f are integers of 1 or more and 10 or less. In the formula (3-1), — (CH ₂ ) _i is bonded to the nitrogen atom of the formula (3), and R ³⁴ is bonded to M of the formula (3).

The structural unit derived from the conjugated diene compound and / or the structural unit derived from the aromatic vinyl compound in R ³⁴ is preferably a structural unit derived from isoprene, a structural unit derived from styrene, or a structural unit derived from butadiene.
f is preferably an integer of 1 to 5.
i is preferably an integer of 2 or more and 4 or less, and more preferably 3.

As the group represented by the above formula (3-1), preferably, R ³⁴ is a structural unit derived from isoprene, i is a group of 1, R ³⁴ represents a structural unit derived from isoprene, and i is 2. A certain group or R ³⁴ represents a structural unit derived from isoprene, and i is a group of 3.
Examples of the alkali metal atom of M include lithium, sodium, potassium and cesium, and lithium is preferable.

Of the compounds represented by formula (3), R ³¹ represents a group represented by formula (3-1), R ²¹ and R ²² each independently represents a hydrocarbyl group, and M represents lithium. As a compound to represent, the compound obtained by making isoprene react with a (dialkylamino) alkyl lithium compound can be mentioned. Examples of such compounds include 3- (dimethylamino) propyllithium, 3- (diethylamino) propyllithium, 3- (dibutylamino) propyllithium, 4- (dimethylamino) butyllithium, 4- (diethylamino) butyllithium. 4- (dipropylamino) butyllithium and 3- (dibutylamino) butyllithium.

Among the compounds represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² are bonded to a part of R ^{21 and} a part of R ^22. The compound obtained by reacting isoprene with an alkyl lithium compound having a cyclic amino group can be exemplified as the compound in which M represents lithium. Examples of the alkyllithium compound having a cyclic amino group include 3- (1-pyrrolidinyl) propyllithium, 3- (1-piperidinyl) propyllithium, 3- (1-hexamethyleneimino) propyllithium and 3- [1- Mention may be made of (1,2,3,6-tetrahydropyridinyl)] propyllithium.

Among the compounds represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² are bonded to a part of R ^{21 and} a part of R ^22. Examples of the compound which represents a hydrocarbylene group having a nitrogen atom and / or an oxygen atom and wherein M represents lithium include compounds obtained by reacting isoprene with an alkyl lithium compound having a cyclic amino group. it can. Examples of the alkyllithium compound having a cyclic amino group include 3- (1-morpholino) propyllithium, 3- (1-imidazolyl) propyllithium and 3- (4,5-dihydro-1-imidazolyl) propyllithium. be able to.

Among the compounds represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² are bonded to a part of R ^{21 and} a part of R ^22. A group having 5 to 20 carbon atoms represented by —Si (R ³⁵ ) ₂ — (CH ₂ ) _x —Si (R ³⁵ ) ₂ — (R ³⁵ represents a hydrocarbyl group, and x is 1 or more The compound in which M represents lithium and 3- (2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl) propyllithium And compounds obtained by reacting isoprene, butadiene or styrene.

Of the compounds represented by the formula (3), R ³¹ represents a group represented by the formula (3-1), and R ²¹ and R ²² are bonded to a part of R ^{21 and} a part of R ^22. A group having 4 to 20 carbon atoms represented by —Si (R ³⁶ ) ₂ — (CH ₂ ) _y — (R ³⁶ represents a hydrocarbyl group, and y is an integer of 2 to 11. The compound in which M represents lithium is obtained by reacting 3- (2,2, -dimethyl-1-aza-2-sila-1-cyclopentyl) propyllithium with isoprene, butadiene or styrene. The compound etc. which can be mentioned can be mentioned.

As the compound represented by formula (3), preferably, R ³¹ represents a group represented by formula (3-1), R ²¹ and R ²² each independently represents a hydrocarbyl group, and M represents More preferably, R ²¹ and R ²² each independently represents an alkyl group having 1 to 4 carbon atoms, M represents lithium, and R ³¹ represents a compound represented by the formula (3-1). R ³⁴ in formula (3-1) represents a structural unit derived from isoprene, f is 1 or more and 5 or less, and i is 2 or more and 4 or less, more preferably Is a compound obtained by reacting 3- (dimethylamino) propyllithium or 3- (diethylamino) propyllithium with isoprene.

Two or more types of compounds represented by formula (3) may be used in combination.

As the polymerization initiator, a conjugated diene polymer having an active end may be used. The conjugated diene polymer having an active end can be obtained by reacting a polymerization initiator and a monomer containing a conjugated diene compound. As the polymerization initiator, the same compounds as those described above can be used. Although the monomer used for the conjugated diene polymer having an active end is not particularly limited, examples of the monomer include the above-described conjugated diene compound, aromatic vinyl compound, and a compound copolymerizable with the conjugated diene compound. Can be used. The conjugated diene polymer having an active end preferably contains only isoprene or isoprene and an aromatic vinyl compound as a monomer unit.

The modifier can include a compound having a structure represented by the formula (5).

In Formula (5), R ¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group, M ¹ represents a silicon atom, a tin atom, a germanium atom, or a phosphorus atom, and L ¹ represents a halogen atom or a hydrocarbyloxy group. And when there are a plurality of R ¹ and L ^{1 s} , they may be the same or different, and when M ¹ is a silicon atom, a tin atom or a germanium atom, n represents 0, and m and l are each independently m represents an integer of 0 to 4 satisfying m + l = 4, and when M ¹ is a phosphorus atom, n represents 0 or 1, and m and l each independently represents an integer of 0 to 3 satisfying m + l = 3.

The alkyl group in R ¹ is preferably an alkyl group having 1 to 12 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl Group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, cyclopentyl group and cyclohexyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, and an isopropenyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group, and a xylyl group.

In L ^1, examples of the halogen atom include chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbyloxy group include an alkoxy group and an aryloxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl Examples thereof include an oxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group.

Examples of the compound having the structure represented by the formula (5), for example, a silane compound M ¹ is a silicon atom, a tin compound M ¹ is a tin atom, M ¹ is the germanium compound and M ¹ is a germanium atom The phosphorus compound which is a phosphorus atom is mentioned.

Examples of the silane compound include silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, methyltrichlorosilane, dimethyldichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, hexyltrichlorosilane, tetramethoxysilane, methyltrimethoxysilane, Dimethoxydimethylsilane, chlorotrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, diethoxydiethylsilane, dichlorodimethoxysilane and trichloromethoxysilane Can be mentioned.
Examples of the tin compound include tin tetrachloride, monomethyltrichlorotin, monoethyltrichlorotin, monobutyltrichlorotin, monophenyltrichlorotin, tetramethoxytin, and tetraethoxytin.
Examples of germanium compounds include germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, methyltrichlorogermanium, ethyltrichlorogermanium, phenyltrichlorogermanium, dimethyldichlorogermanium, diethyldichlorogermanium, dibutyldichlorogermanium, diphenyldichlorogermanium, tetra Mention may be made of methoxygermanium, tetraethoxygermanium, tetraisopropoxygermanium and tetrabutoxygermanium.
Examples of phosphorus compounds include phosphorus halide compounds such as trichlorophosphine and tribromophosphine, phosphite compounds such as trisnonylphenyl phosphite, trimethyl phosphite, and triethyl phosphite, trimethyl phosphate, and triethyl phosphate. A phosphate ester compound is mentioned.

The amount of the polymerization initiator used is preferably 0.01 mmol to 15 mmol per 100 g of the total amount of monomers.

The polymerization of the monomer is preferably performed in a hydrocarbon solvent. As the hydrocarbon solvent, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and the like can be used. A hydrocarbon solvent may be used individually or in combination of 2 or more types, and a mixture of aliphatic hydrocarbon and alicyclic hydrocarbon such as industrial hexane may be used.

Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, 2-methylpentane, 3-methylpentane, n-hexane, propene, 1-butene and iso-butene. , Trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene and 2-hexene. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane, cyclohexane, and methylcyclopentane.

When the monomer is polymerized in the solvent, the concentration of the monomer in the solvent is usually 1 to 50% by mass, preferably 5 to 30% by mass. The polymerization temperature is usually 25 to 100 ° C., preferably 35 to 90 ° C., more preferably 50 to 80 ° C. The polymerization time is usually 10 minutes to 5 hours.

The conjugated diene polymer according to this embodiment may have a unit based on a compound having a hetero atom and / or a silicon atom as a modifier at either the terminal or the molecular chain of the polymer. The unit may be present both at the end of the polymer and / or in the molecular chain.

As the modifier, a compound having a structure represented by the formula (7) can be used. The compound has a functional group copolymerizable with a conjugated diene compound. Conjugation having a unit based on a compound having a structure represented by formula (7) in a molecular chain by polymerizing a monomer containing a compound having a structure represented by formula (7) together with a conjugated diene compound A diene polymer can be obtained.

In the formula (7), R ⁷¹ represents a hydrogen atom or a hydrocarbyl group, s represents 0 or 1 (an integer of 0 to 1), R ⁷² represents a hydrocarbylene group, and X ⁷ , X ⁸ and X ⁹ Each independently represents a substituted amino group or an optionally substituted hydrocarbyl group, and at least one of X ⁷ , X ⁸ and X ⁹ is a substituted amino group.

Examples of the hydrocarbyl group for R ⁷¹ include an alkyl group, an alkenyl group, and an aryl group.
As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof 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. Preferably, it is a methyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, and an isopropenyl group, and a vinyl group is preferable. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a methylphenyl group, and an ethylphenyl group, and a phenyl group is preferable.
R ⁷¹ is preferably a hydrogen atom, a methyl group, a vinyl group, or a phenyl group, and more preferably a hydrogen atom.

Examples of the hydrocarbylene group for R ⁷² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.
As the alkylene group, an alkylene group having 2 to 6 carbon atoms is preferable, and examples thereof include a methylene group, an ethylene group, and a trimethylene group, and a methylene group or an ethylene group is more preferable. As the arylene group, an arylene group having 5 to 12 carbon atoms is preferable, and examples thereof include a phenylene group, a naphthylene group, and a biphenylene group, and a phenylene group is more preferable. Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. A group in which a phenylene group and an alkylene group are bonded is preferable.
As the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the arylene group of the group is bonded to the carbon atom to which R ^{71 in} the formula (7) is bonded.

Examples of the group in which the phenylene group and the alkylene group are bonded (phenylene-alkylene group) include a group represented by the formula (7-R).

In the formula, d represents an integer of 1 to 10.

Examples of the phenylene-alkylene group include a para-phenylene-alkylene group, a meta-phenylene-alkylene group, and an ortho-phenylene-alkylene group depending on the position of the carbon atom on the benzene ring to which the alkylene group is bonded. In the case of a group represented by the formula (7-R), the para-phenylene-alkylene group is a group represented by the formula (7-Ra), and the meta-phenylene-alkylene group is represented by the formula (7-Rb). The ortho-phenylene-alkylene group is a group represented by the formula (7-Rc).

In the formula, d1, d2 and d3 each independently represents an integer of 1 to 10.

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), more preferably a group represented by the formula (7-Ra) Or a group represented by the formula (7-Rb), more preferably a para-phenylene-methylene group (a group represented by the formula (7-Ra) where d1 = 1), a meta-phenylene-methylene group. (Group represented by formula (7-Rb) where d2 = 1), para-phenylene-ethylene group (group represented by formula (7-Ra) where d1 = 2) or meta-phenylene-ethylene group (Group represented by formula (7-Rb) where d2 = 2).

Examples of the hydrocarbyl group which may have a substituent in X ⁷ , X ⁸ and X ⁹ include a hydrocarbyl group and a substituted hydrocarbyl group.

Examples of the hydrocarbyl group of X ⁷ , X ⁸ and X ⁹ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof 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. Can do. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, and an isopropenyl group. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and examples thereof include an ethynyl group and a 2-propynyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a xylyl group. The aralkyl group is preferably an aralkyl group having 7 to 13 carbon atoms, and examples thereof include a benzyl group. The hydrocarbyl group is preferably an alkyl group.

Examples of the substituted hydrocarbyl group of X ⁷ , X ⁸ and X ⁹ include a group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom.
Examples of the substituted hydrocarbyl group having an oxygen atom include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.
Examples of the substituted hydrocarbyl group having a nitrogen atom include dialkylaminoalkyl groups such as a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, and a diethylaminoethyl group.
Examples of the substituted hydrocarbyl group having a silicon atom include trialkylsilylalkyl groups such as a trimethylsilylmethyl group, a trimethylsilylethyl group, a triethylsilylmethyl group, and a triethylsilylethyl group.

The number of carbon atoms of the hydrocarbyl group which may have a substituent is preferably 1 to 10, and more preferably 1 to 4. The hydrocarbyl group which may have a substituent is preferably an alkyl group or an alkoxyalkyl group. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 4 carbon atoms.

Examples of the substituted amino group in X ⁷ , X ⁸ and X ⁹ include a group represented by the formula (7-X) and a group represented by the formula (7-Y).

In the formula (7-X), R ⁷³ and R ⁷⁴ each independently represents a hydrocarbyl group or a trihydrocarbylsilyl group, or a nitrogen atom formed by bonding a part of R ^{73 and} a part of R ⁷⁴ The hydrocarbylene group which may have an atom and / or an oxygen atom is represented.

In the formula (7-Y), R ⁷⁵ represents a hydrocarbylidene group. In the formula (7-X), R ⁷⁵ is a group corresponding to a group in which R ⁷³ and R ⁷⁴ are one group and bonded to the nitrogen atom with a double bond.

Examples of the hydrocarbyl group in R ⁷³ and R ⁷⁴ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof 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. Can do. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, and an isopropenyl group. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and examples thereof include an ethynyl group and a 2-propynyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a xylyl group. The aralkyl group is preferably an aralkyl group having 7 to 13 carbon atoms, and examples thereof include a benzyl group.

The number of carbon atoms in the hydrocarbyl group is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 to 2. The hydrocarbyl group is preferably an alkyl group, more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group in R ⁷³ and R ⁷⁴ include trialkylsilyl groups having 3 to 12 carbon atoms such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyl-dimethylsilyl group. be able to.

The trihydrocarbylsilyl group is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably a trialkyl in which the alkyl group bonded to the silicon atom is an alkyl group having 1 to 3 carbon atoms. A silyl group, more preferably a trimethylsilyl group.

Examples of the hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom in which a part of R ^{73 and} a part of R ⁷⁴ are bonded include a hydrocarbylene group and a nitrogen atom-containing hydrocarbylene. Groups and oxygen atom-containing hydrocarbylene groups.
As a hydrocarbylene group, alkylene groups, such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, can be mentioned, for example.
Examples of the nitrogen atom-containing hydrocarbylene group include a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH— A group represented by N═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified.
Examples of the oxygen atom-containing hydrocarbylene group include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom is preferably 2 to 20, more preferably 2 to 7, and still more preferably 4 to 6.

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom is preferably a hydrocarbylene group, more preferably an alkylene group, and still more preferably a polymethylene group.

R ⁷³ and R ⁷⁴ are preferably each independently an alkyl group or a trialkylsilyl group, or an alkylene group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded, more preferably each independently. Is an alkyl group.

Examples of the group represented by the formula (7-X) include an acyclic amino group and a cyclic amino group.

Among the acyclic amino groups, the groups in which R ⁷³ and R ⁷⁴ are hydrocarbyl groups in the formula (7-X) include, for example, dimethylamino group, diethylamino group, di (n-propyl) amino group, di (isopropyl) Examples thereof include dialkylamino groups such as amino group, di (n-butyl) amino group, di (sec-butyl) amino group, di (tert-butyl) amino group, and ethylmethylamino group.
Of the acyclic amino groups, the groups in which R ⁷³ and R ⁷⁴ are trihydrocarbylsilyl groups in the formula (7-X) include, for example, bis (trimethylsilyl) amino group, bis (tert-butyl-dimethylsilyl) amino group And bis (trialkylsilyl) amino groups such as

Among the cyclic amino groups, in the formula (7-X), the group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded is a hydrocarbylene group, for example, a 1-aziridinyl group, 1- Examples thereof include azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group and 1-pyrrolyl group.
Of the cyclic amino groups, in the formula (7-X), a group in which a part of R ^{73 and} a part of R ⁷⁴ are bonded is a nitrogen atom-containing hydrocarbylene group, for example, a 1-imidazolyl group 4,5-dihydro-1-imidazolyl group, 1-imidazolidinyl group and 1-piperazinyl group.
Among the cyclic amino groups, a group in which a part of R ^{73 and} a part of R ^{74 in} the formula (7-X) is an oxygen atom-containing hydrocarbylene group includes a morpholino group. it can.

Examples of the hydrocarbylidene group for R ⁷⁵ include an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, and a 1,3-dimethylbutylidene group.
The number of carbon atoms of the hydrocarbylidene group is preferably 2 to 20, and more preferably 2 to 6.

Examples of the group represented by the formula (7-Y) include ethylideneamino group, 1-methylpropylideneamino group, 1,3-dimethylbutylideneamino group, 1-methylethylideneamino group, 4-N, N And acyclic amino groups such as dimethylaminobenzylideneamino group.

In the formula (7), the substituted amino group in X ⁹ , X ⁹ and X ⁹ is preferably an acyclic amino group, more preferably a dialkylamino group, still more preferably a dimethylamino group, a diethylamino group, A di (n-propyl) amino group or a di (n-butyl) amino group, particularly preferably a dimethylamino group or a diethylamino group.

In the formula (7), at least one of X ⁷ , X ⁸ and X ⁹ is a substituted amino group, preferably two or more of X ⁷ , X ⁸ and X ⁹ are substituted amino groups, more preferably , X ⁷ , X ⁸ and X ⁹ are substituted amino groups.

Among the compounds represented by the formula (7), the following compounds may be mentioned as compounds in which R ⁷¹ is a hydrogen atom and one of X ⁷ , X ⁸ and X ⁹ is a dialkylamino group.

Examples of the compound in which s in Formula (7) is 0 include (dimethylamino) dimethylvinylsilane, (diethylamino) dimethylvinylsilane, (dipropylamino) dimethylvinylsilane, (dibutylamino) dimethylvinylsilane, and (dimethylamino) diethyl. Examples include vinyl silane, (diethylamino) diethylvinylsilane, (dipropylamino) diethylvinylsilane and (dibutylamino) diethylvinylsilane.

Examples of the compound in which s is 1 in the formula (7) include (dimethylamino) dimethyl (4-vinylphenyl) silane, (dimethylamino) dimethyl (3-vinylphenyl) silane, (diethylamino) dimethyl (4- Vinylphenyl) silane, (diethylamino) dimethyl (3-vinylphenyl) silane, (dipropylamino) dimethyl (4-vinylphenyl) silane, (dipropylamino) dimethyl (3-vinylphenyl) silane, (dibutylamino) dimethyl (4-vinylphenyl) silane, (dibutylamino) dimethyl (3-vinylphenyl) silane, (dimethylamino) diethyl (4-vinylphenyl) silane, (dimethylamino) diethyl (3-vinylphenyl) silane, (diethylamino) Diethyl (4-vinylphenyl) sila , (Diethylamino) diethyl (3-vinylphenyl) silane, (dipropylamino) diethyl (4-vinylphenyl) silane, (dipropylamino) diethyl (3-vinylphenyl) silane, (dibutylamino) diethyl (4-vinyl Phenyl) silane and (dibutylamino) diethyl (3-vinylphenyl) silane.

Among the compounds represented by formula (7), the following compounds may be mentioned as compounds in which R ⁷¹ is a hydrogen atom and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

Examples of the compound in which s in the formula (7) is 0 include bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (dipropylamino) methylvinylsilane, bis (dibutylamino) methylvinylsilane, bis Examples include (dimethylamino) ethylvinylsilane, bis (diethylamino) ethylvinylsilane, bis (dipropylamino) ethylvinylsilane, and bis (dibutylamino) ethylvinylsilane.

Examples of the compound in which s is 1 in the formula (7) include bis (dimethylamino) methyl (4-vinylphenyl) silane, bis (dimethylamino) methyl (3-vinylphenyl) silane, and bis (diethylamino) methyl. (4-vinylphenyl) silane, bis (diethylamino) methyl (3-vinylphenyl) silane, bis (dipropylamino) methyl (4-vinylphenyl) silane, bis (dipropylamino) methyl (3-vinylphenyl) silane Bis (dibutylamino) methyl (4-vinylphenyl) silane, bis (dibutylamino) methyl (3-vinylphenyl) silane, bis (dimethylamino) ethyl (4-vinylphenyl) silane, bis (dimethylamino) ethyl ( 3-vinylphenyl) silane, bis (diethylamino) ethyl (4 Vinylphenyl) silane, bis (diethylamino) ethyl (3-vinylphenyl) silane, bis (dipropylamino) ethyl (4-vinylphenyl) silane, bis (dipropylamino) ethyl (3-vinylphenyl) silane, bis ( Examples include dibutylamino) ethyl (4-vinylphenyl) silane and bis (dibutylamino) ethyl (3-vinylphenyl) silane.

Of the compounds represented by formula (7), as the compound R ⁷¹ is two are dialkylamino group of X ^7, X ⁸ and X ⁹ are methyl groups, it may be mentioned the following compounds.

Examples of the compound in which s is 1 in the formula (7) include bis (dimethylamino) methyl (4-isopropenylphenyl) silane, bis (dimethylamino) methyl (3-isopropenylphenyl) silane, and bis (diethylamino). ) Methyl (4-isopropenylphenyl) silane, bis (diethylamino) methyl (3-isopropenylphenyl) silane, bis (dipropylamino) methyl (4-isopropenylphenyl) silane, bis (dipropylamino) methyl (3 -Isopropenylphenyl) silane, bis (dibutylamino) methyl (4-isopropenylphenyl) silane, bis (dibutylamino) methyl (3-isopropenylphenyl) silane, bis (dimethylamino) ethyl (4-isopropenylphenyl) Silane, bis (dimethylamino ) Ethyl (3-isopropenylphenyl) silane, bis (diethylamino) ethyl (4-isopropenylphenyl) silane, bis (diethylamino) ethyl (3-isopropenylphenyl) silane, bis (dipropylamino) ethyl (4-iso Propenylphenyl) silane, bis (dipropylamino) ethyl (3-isopropenylphenyl) silane, bis (dibutylamino) ethyl (4-isopropenylphenyl) silane and bis (dibutylamino) ethyl (3-isopropenylphenyl) silane Is mentioned.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a vinyl group and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

Examples of the compound in which s in Formula (7) is 0 include, for example, bis (dimethylamino) methyl (1-methylene-2-propenyl) silane, bis (diethylamino) methyl (1-methylene-2-propenyl) silane, Bis (dipropylamino) methyl (1-methylene-2-propenyl) silane, bis (dibutylamino) methyl (1-methylene-2-propenyl) silane, bis (dimethylamino) ethyl (1-methylene-2-propenyl) Silane, bis (diethylamino) ethyl (1-methylene-2-propenyl) silane, bis (dipropylamino) ethyl (1-methylene-2-propenyl) silane and bis (dibutylamino) ethyl (1-methylene-2-propenyl) ) Silane.

Examples of the compound represented by formula (7) include the following compounds as compounds in which R ⁷¹ is a phenyl group and two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

Examples of the compound in which s is 1 in the formula (7) include 1- {4- [bis (dimethylamino) methylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis (diethylamino) methylsilyl] Phenyl} -1-phenylethylene, 1- {4- [bis (dipropylamino) methylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis (dibutylamino) methylsilyl] phenyl} -1-phenylethylene 1- {4- [bis (dimethylamino) ethylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis (diethylamino) ethylsilyl] phenyl} -1-phenylethylene, 1- {4- [bis ( Dipropylamino) ethylsilyl] phenyl} -1-phenylethylene and 1- {4- [bis (dibutylamino) ethyl Rushiriru] phenyl} -1-phenyl ethylene.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a hydrogen atom and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

Examples of the compound in which s in Formula (7) is 0 include tris (dimethylamino) vinylsilane, tris (diethylamino) vinylsilane, tris (dipropylamino) vinylsilane, and tris (dibutylamino) vinylsilane.

Examples of the compound in which s is 1 in the formula (7) include tris (dimethylamino) (4-vinylphenyl) silane, tris (dimethylamino) (3-vinylphenyl) silane, tris (diethylamino) (4- Vinylphenyl) silane, tris (diethylamino) (3-vinylphenyl) silane, tris (dipropylamino) (4-vinylphenyl) silane, tris (dipropylamino) (3-vinylphenyl) silane, tris (dibutylamino) (4-vinylphenyl) silane and tris (dibutylamino) (3-vinylphenyl) silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a methyl group and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.
Examples of the compound in which s is 1 in the formula (7) include tris (dimethylamino) (4-isopropenylphenyl) silane, tris (dimethylamino) (3-isopropenylphenyl) silane, tris (diethylamino) ( 4-isopropenylphenyl) silane, tris (diethylamino) (3-isopropenylphenyl) silane, tris (dipropylamino) (4-isopropenylphenyl) silane, tris (dipropylamino) (3-isopropenylphenyl) silane And tris (dibutylamino) (4-isopropenylphenyl) silane and tris (dibutylamino) (3-isopropenylphenyl) silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a vinyl group and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

Examples of the compound in which s is 0 in the formula (7) include tris (dimethylamino) (1-methylene-2-propenyl) silane, tris (diethylamino) (1-methylene-2-propenyl) silane, tris ( Dipropylamino) (1-methylene-2-propenyl) silane and tris (dibutylamino) (1-methylene-2-propenyl) silane.

Examples of the compound represented by the formula (7) include the following compounds as compounds in which R ⁷¹ is a phenyl group and three of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups.

Examples of the compound in which s is 1 in the formula (7) include 1- [4-tris (dimethylamino) silylphenyl] -1-phenylethylene, 1- [4-tris (diethylamino) silylphenyl] -1 -Phenylethylene, 1- [4-tris (di-n-propylamino) methylsilylphenyl] -1-phenylethylene and 1- [4-tris (di-n-butylamino) methylsilylphenyl] -1-phenyl Ethylene is mentioned.

A preferable compound represented by the group represented by the formula (7) is a compound in which two of X ⁷ , X ⁸ and X ^{9 in} the formula (7) are dialkylamino groups, and more preferably the compound represented by the formula (7). A compound in which two of X ⁷ , X ⁸ and X ⁹ are dialkylamino groups, R ⁷¹ is a hydrogen atom and s is 0.

Most preferably, the compound represented by the formula (7) is bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (dipropylamino) methylvinylsilane, bis (dibutylamino) methylvinylsilane, bis (dimethylamino). ) Ethyl vinyl silane, bis (diethylamino) ethyl vinyl silane, bis (dipropylamino) ethyl vinyl silane, bis (dibutylamino) ethyl vinyl silane.

As the modifier, a compound having a structure represented by the formula (6) can be used. Based on a compound having a structure represented by formula (6) by reacting a polymer obtained by polymerizing a monomer containing a conjugated diene compound with a compound having a structure represented by formula (6). A conjugated diene polymer having a terminal at the end can be obtained.

In formula (6), X ¹ , X ² and X ³ each independently represent a hydrocarbyl group, a hydrocarbyloxy group, a halogen atom, or a functional group capable of reacting with the active end of the conjugated diene polymer, R ⁶¹ And R ⁶² each independently represents a hydrogen atom or a hydrocarbyl group, and when there are a plurality of R ⁶¹ and R ⁶² , they may be the same or different. A ¹ represents an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a silicon atom (any one of an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom or a silicon atom) Or A ¹ may have a ring structure, and a part of the structure of X ¹ , X ² or X ³ may be bonded to a part of A ^1. Good. That is, A ¹ may be bonded to the silicon atom in formula (6) via X ¹ , X ² or X ³ . a represents an integer of 0 to 10.

Examples of the hydrocarbyl group in X ¹ , X ² and X ³ include an alkyl group, an aryl group, an alkenyl group and an aralkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples include n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, cyclopentyl group and cyclohexyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group, and a xylyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, and an isopropenyl group. Examples of the aralkyl group include a benzyl group.
Examples of the hydrocarbyloxy group include an alkoxy group and an aryloxy group. The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms, such as a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group. Is mentioned. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. The hydrocarbyloxy group is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
As a halogen atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the functional group capable of reacting with the active terminal of the conjugated diene polymer include a hydrocarbon group having an epoxy group and a hydrocarbon group having a carbonyl group.

The hydrocarbyl group in R ⁶¹ and R ⁶² is preferably a hydrocarbyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group. is there. If R ⁶¹ is plural, R ⁶¹ may be different be the same as each other, if R ⁶² is plural, R ⁶² may be different be the same as each other.
a is preferably 3 or more from the viewpoint of improving fuel economy, and is preferably 4 or less from the viewpoint of improving economy during production.

Examples of A ¹ that is an organic group having at least a nitrogen atom include a group represented by the formula (6-1).

In the formula (6-1), R ⁶³ and R ⁶⁴ each independently represents a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or a part of R ⁶³ and one of R ⁶⁴ The hydrocarbylene group which may have at least 1 type of atom selected from the atomic group which consists of a silicon atom, a nitrogen atom, and an oxygen atom formed by combining with a part.

Here, when a part of R ^{63 and} a part of R ⁶⁴ are not bonded, the group represented by the formula (6-1) is an acyclic amino group, and R ⁶³ and R ⁶⁴ are bonded to each other. In this case, it is a cyclic amino group.

The hydrocarbyl group which may have a substituent in R ⁶³ and R ⁶⁴ is a hydrocarbyl group or a substituted hydrocarbyl group.
Examples of the hydrocarbyl group include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group; carbon atoms such as vinyl group, allyl group and isopropenyl group. An alkenyl group having 2 to 12 carbon atoms; an aryl group having 6 to 12 carbon atoms such as a phenyl group and a benzyl group can be mentioned, preferably an alkyl group or an aryl group, more preferably a methyl group, an ethyl group or a benzyl group. It is a group.
Examples of the substituted hydrocarbyl group include oxacycloalkyl groups such as an oxiranyl group and a tetrahydrofuranyl group, and a tetrahydrofuranyl group is preferable.

In this specification, the oxacycloalkyl group represents a group in which CH ₂ on the alicyclic ring of the cycloalkyl group is replaced with an oxygen atom.

Examples of the trihydrocarbylsilyl group in R ⁶³ and R ⁶⁴ include a trimethylsilyl group and a tert-butyl-dimethylsilyl group, and a trimethylsilyl group is preferable.

A hydrocarbylene group which may have at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom, formed by bonding a part of R ^{63 and} a part of R ⁶⁴ , A carbylene group or a hydrocarbylene group (heteroatom-containing hydrocarbylene group) having at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom.
Examples of the hydrocarbylene group include alkylene groups having 2 to 12 carbon atoms such as a tetramethylene group, a pentamethylene group, a hexamethylene group, and a 2,2,4-trimethylhexane-1,6-diyl group. Among them, an alkylene group having 4 to 7 carbon atoms is preferable, and a pentamethylene group or a hexamethylene group is particularly preferable.
Examples of the heteroatom-containing hydrocarbylene group include a silicon atom-containing hydrocarbylene group, a nitrogen atom-containing hydrocarbylene group, and an oxygen atom-containing hydrocarbylene group.
Examples of the silicon atom-containing hydrocarbylene group include a group represented by —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —Si (CH ₃ ) ₂ —. Examples of the nitrogen atom-containing hydrocarbylene group include a group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ —. Examples of the oxygen atom-containing hydrocarbylene group include a group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.

Examples of A ¹ that is an organic group having at least an oxygen atom include a group represented by the formula (6-2).

In the formula (6-2), X ⁴ represents a hydrocarbylene group having 1 to 6 carbon atoms which may have an oxygen atom, and R ⁶⁵ represents a hydrogen atom or a hydrocarbyl having 1 to 6 carbon atoms. Represents a group.

Examples of the hydrocarbylene group having 1 to 6 carbon atoms which may have an oxygen atom in X ⁴ include, for example, an unsubstituted hydrocarbylene group and a group having an oxygen atom as a substituent. Mention may be made of hydrocarbylene groups.
Specific examples of X ⁴ include a hydrocarbylene group and a hydrocarbyleneoxy group, and more specifically, an ethylene group, a propylene group, a butylene group, a 1-oxyethylene group, a 1-oxytrine group. Mention may be made of methylene and 1-oxytetramethylene groups. X ⁴ is preferably a 1-oxytrimethylene group.

Examples of the hydrocarbyl group having 1 to 6 carbon atoms in R ⁶⁵ include an alkyl group and an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n group Examples include -butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, isopentyl group, n-hexyl group, cyclohexyl group and phenyl group. R ⁶⁵ is preferably a hydrogen atom or a methyl group.

Examples of A ¹ that is an organic group having at least a sulfur atom include a group represented by the formula (6-3).

In formula (6-3), R ⁶⁶ represents a trihydrocarbylsilyl group. Examples of the trihydrocarbylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyl-dimethylsilyl group, preferably a trimethylsilyl group or a triethylsilyl group.

Examples of A ¹ that is an organic group having at least a silicon atom include a group represented by the formula (6-4). That is, the compound represented by the formula (6), for example, a polyorganosiloxane compound having a group represented by the formula (6-4) as A ^1.

In formula (6-4), R ⁶⁶ , R ⁶⁷ and R ⁶⁸ each independently represent a hydrocarbyl group or a group having a repeating unit of hydrocarbyleneoxy group, and X ⁵ and X ⁶ each independently represent A hydrocarbyl group, a hydrocarbyloxy group, a group containing a repeating unit of a hydrocarbyleneoxy group, a halogen atom, or a functional group capable of reacting with an active terminal of a conjugated diene polymer and / or a modifier, and g is 0 Represents an integer of ˜600, and a plurality of R ⁶⁶ and X ⁵ may be the same or different.

Examples of the hydrocarbyl group in R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , X ⁵ and X ⁶ include an alkyl group, an aryl group and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- Examples include pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, cyclopentyl group and cyclohexyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a tolyl group, and a xylyl group. As the aralkyl group, an aralkyl group having 7 to 13 carbon atoms is preferable, and examples thereof include a benzyl group.
Examples of the group having a repeating unit of hydrocarbyleneoxy group in R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , X ⁵ and X ⁶ include a group having a repeating unit based on alkylene glycol. Examples of the hydrocarbyleneoxy group include a 1-oxyethylene group, a 1-oxytrimethylene group, and a 1-oxytetramethylene group, and a 1-oxyethylene group is preferable.

In X ⁵ and X ^6, as the hydrocarbyloxy group, for example, an alkoxy group and aryloxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl Examples thereof include an oxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group.
As a halogen atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the functional group capable of reacting with the active terminal of the conjugated diene polymer and / or the modifier include a group having 4 to 12 carbon atoms having an epoxy group and a hydrocarbon group having a carbonyl group.

Examples of the group having 4 to 12 carbon atoms having an epoxy group include a group represented by the following formula (6-4-1).
-Z ¹ -Z ² -E (6-4-1)
In formula (6-4-1), Z ¹ represents an alkylene group having 1 to 10 carbon atoms or an alkylarylene group, Z ² represents a methylene group, a sulfur atom or an oxygen atom, and E represents a carbon having an epoxy group. A hydrocarbon group of 2 to 10.

Examples of the group represented by the formula (6-4-1), preferably a group Z ² is an oxygen atom, Z ² is an oxygen atom, and is more preferably a group E is a glycidyl group, Z ¹ Is particularly preferably a group in which is an alkylene group having 1 to 3 carbon atoms, Z ² is an oxygen atom, and E is a glycidyl group.

G is preferably 3 to 360 from the viewpoint of handling, and preferably 4 to 120 from the viewpoint of fuel saving performance.

Among the compounds having the structure represented by the formula (6), as the compound in which A ¹ is an acyclic amino group represented by the formula (6-1), for example, [3- (dimethylamino) propyl] trimethoxy Silane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] tri Methoxysilane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (dimethylamino) propyl] methyldimethoxysilane, [3- (diethylamino) propyl] methyldimethoxysilane, [3- (dimethylamino) propyl ] Ethyldimethoxysilane, [3- (diethylamino) propyl] ethyldimeth Xysilane, [3- (dimethylamino) propyl] dimethylmethoxysilane, [3- (dimethylamino) propyl] diethylmethoxysilane, [3- (diethylamino) propyl] dimethylmethoxysilane, [3- (diethylamino) propyl] diethylmethoxy Silane, [(3-methyl-3-ethylamino) propyl] methyldimethoxysilane, [(3-methyl-3-ethylamino) propyl] ethyldimethoxysilane, [3- (dimethylamino) propyl] methyldiethoxysilane, [3- (Diethylamino) propyl] methyldiethoxysilane, [3- (dimethylamino) propyl] ethyldiethoxysilane, [3- (diethylamino) propyl] ethyldiethoxysilane, [3- (dimethylamino) propyl] dimethyl Ethoxysila [3- (dimethylamino) propyl] diethylethoxysilane, [3- (diethylamino) propyl] dimethylethoxysilane, [3- (diethylamino) propyl] diethylethoxysilane, [3- (ethylmethylamino) propyl] methyldi Ethoxysilane, [3- (ethylmethylamino) propyl] ethyldiethoxysilane, [3- (benzylmethylamino) propyl] trimethoxysilane, [3- (benzylmethylamino) propyl] triethoxysilane, {3- [ Di (methoxymethyl) amino] propyl} trimethoxysilane, {3- [di (methoxyethyl) amino] propyl} trimethoxysilane, {3- [di (methoxymethyl) amino] propyl} triethoxysilane, {3- [Di (methoxyethyl) amino] propyl} Liethoxysilane, {3- [di (ethoxyethyl) amino] propyl} trimethoxysilane, {3- [di (ethoxymethyl) amino] propyl} trimethoxysilane, {3- [di (ethoxyethyl) amino] propyl ] Triethoxysilane, {3- [di (ethoxymethyl) amino] propyl} triethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl} trimethoxysilane, {3- [N, N- Bis (trimethylsilyl) amino] propyl} triethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} trimethoxysilane, {3- [N, N-bis (t-butyldimethyl) Silyl) amino] propyl} triethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl } Methyldimethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl} methyldiethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} methyldimethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} methyldiethoxysilane, {3- [N, N-bis (trimethylsilyl) amino] propyl} dimethylmethoxysilane, {3- [N , N-bis (trimethylsilyl) amino] propyl} dimethylethoxysilane, {3- [N, N-bis (t-butyldimethylsilyl) amino] propyl} dimethylmethoxysilane, {N, N-bis- [di (t -Butyldimethylsilyl) amino] propyl} dimethylethoxysilane, [3- (ethylmethylamino) propiyl ] Trimethoxysilane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] methyldimethoxysilane, [3- (ethylmethylamino) propyl] ethyldimethoxysilane, [3- Mention may be made of (ethylmethylamino) propyl] methyldiethoxysilane and [3- (ethylmethylamino) propyl] ethyldiethoxysilane.

Among the compounds having the structure represented by the formula (6), the compound in which A ¹ is an acyclic amino group represented by the formula (6-1) is [3- ( Dimethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane or [3- (diethylamino) propyl] triethoxysilane are preferred.

Of the compounds having the structure represented by the formula (6), examples of the compound in which A ¹ is a cyclic amino group represented by the formula (6-1) include 3-morpholinopropyltrimethoxysilane and 3-morpholinopropyl. Triethoxysilane, 3-morpholinopropylmethyldimethoxysilane, 3-morpholinopropylethyldimethoxysilane, 3-morpholinopropylmethyldiethoxysilane, 3-morpholinopropylethyldiethoxysilane, 3-piperidinopropyltrimethoxysilane, 3- Piperidinopropyltriethoxysilane, 3-piperidinopropylmethyldimethoxysilane, 3-piperidinopropylethyldimethoxysilane, 3-piperidinopropylmethyldiethoxysilane, 3-piperidinopropylethyldiethoxysilane, N- (3-trimet Xylylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole, N- ( 3-triethoxysilylpropyl) -4,5-imidazole, 3-hexamethyleneiminopropyltrimethoxysilane, 3-hexamethyleneiminopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldimethoxysilane, 3-hexamethyleneiminopropyl Mention may be made of ethyldimethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane and 3-hexamethyleneiminopropylethyldiethoxysilane.

Of the compounds having the structure represented by formula (6), a compound in which A ¹ is a cyclic amino group represented by formula (6-1) is N- (3- Trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole or N- (3-Triethoxysilylpropyl) -4,5-imidazole is preferred.

Among the compounds having the structure represented by the formula (6), examples of the compound in which A ¹ is a group represented by the formula (6-2) include 3-glycidoxypropyltrimethoxysilane, 3-glycol. Cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropylethyldiethoxysilane be able to.

Among the compounds having the structure represented by the formula (6), the compound in which A ¹ is a group represented by the formula (6-2) includes a viewpoint of improving fuel economy, availability of the compound, and long-term storage. From the viewpoint of enhancing stability, 3-glycidoxypropyltrimethoxysilane is preferred.

Among the compounds having the structure represented by the formula (6), examples of the compound in which A ¹ is a group represented by the formula (6-3) include S-trimethylsilylmercaptopropyltrimethoxysilane and S-trimethylsilylmercapto. Propyltriethoxysilane, S-trimethylsilylmercaptopropylmethyldimethoxysilane, S-trimethylsilylmercaptopropylmethyldiethoxysilane, S-triethylsilylmercaptopropyltrimethoxysilane, S-triethylsilylmercaptopropyltriethoxysilane, S-triethylsilylmercaptopropyl Mention may be made of methyldimethoxysilane and S-triethylsilylmercaptopropylmethyldiethoxysilane.

Among the compounds having the structure represented by the formula (6), examples of the compound in which A ¹ is a group represented by the formula (6-4) include diglycidoxypolydimethylsiloxane and dimethyl (methoxy-methylsiloxane). ) Polydimethylsiloxane, dimethyl (acetoxy-methylsiloxane) polydimethylsiloxane, diglycidyl polysiloxane and dichloropolydimethylsiloxane.

Examples of the compound having the structure represented by the formula (6) other than the above compound include tris [3- (trimethoxysilyl) propyl] isocyanurate, tris [3- (triethoxysilyl) propyl] isocyanurate, tris And tris [(alkoxysilyl) alkyl] isocyanurate compounds such as [3- (tripropoxysilyl) propyl] isocyanurate and tris [3- (tributoxysilyl) propyl] isocyanurate. Among them, the compound represented by the formula (6) is preferably tris [3- (trialkoxysilyl) propyl] isocyanurate, and tris [3- (trialkoxy) in which the alkoxy group is an alkoxy group having 1 to 4 carbon atoms. Silyl) propyl] isocyanurate is more preferred, and tris [3- (trimethoxysilyl) propyl] isocyanurate is even more preferred.

Examples of compounds having the structure represented by the formula (6) other than the above compounds include 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl). ) Propyl] piperazine, bis [3- (trimethoxysilyl) propyl] -N-trimethylsilylamine, bis [3- (triethoxysilyl) propyl] -N-trimethylsilylamine, bis [3- (trimethoxysilyl) propyl] Methylamine, bis [3- (triethoxysilyl) propyl] methylamine, bis [3- (trimethoxysilyl) propyl] ethylamine, bis [3- (triethoxysilyl) propyl] ethylamine, tris (trimethoxysilylmethyl) Amine, tris (triethoxysilylmethyl) amine, 2,2-dimethoxy 1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, N- [2- (Trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine, 2- [3- (trimethoxysilyl) propyl] -1,3-dimethylimidazolidine And 2- [3- (trimethoxysilyl) propyl] -1,3- (bistrimethylsilyl) imidazolidine.

As the modifier, a compound having a structure represented by the formula (8) can be used. Based on a compound having a structure represented by formula (8) by reacting a polymer obtained by polymerizing a monomer containing a conjugated diene compound with a compound having a structure represented by formula (8). A conjugated diene polymer having a terminal at the end can be obtained.

In formula (8), R ⁸¹ and R ⁸² each independently represents a hydrocarbyl group which may have a substituent, or a part of R ^{81 and} a part of R ⁸² are bonded to each other. R ⁸⁴ represents a hydrocarbyl group optionally having a nitrogen atom and / or an oxygen atom, and R ⁸⁴ represents a hydrocarbyl group optionally having a substituent, or a hydrogen atom, or R ⁸¹ and A hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom is formed by combining any one of R ⁸² and a part of R ⁸⁴ . R ⁸³ represents a divalent group, and n is 0 or 1.

The hydrocarbyl group which may have a substituent in R ⁸¹ , R ⁸² and R ⁸⁴ is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a hydrocarbyl group substituted with a hydrocarbyloxy group, a hydrocarbyl group substituted with a substituted amino group, and the like.

Examples of the hydrocarbyl group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- A pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, cyclopentyl group and cyclohexyl group can be exemplified. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, and an isopropenyl group. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and examples thereof include an ethynyl group and a 2-propynyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a tolyl group, and a xylyl group. The aralkyl group is preferably an aralkyl group having 7 to 13 carbon atoms, and examples thereof include a benzyl group.

Examples of the hydrocarbyl group substituted with a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group.

Examples of the hydrocarbyl group substituted with a substituted amino group include N, N-dimethylaminomethyl group, 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, 3- (N, N-dimethylamino) alkyl groups such as (N, N-dimethylamino) propyl group and 3- (N, N-diethylamino) propyl group; 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dialkylamino) aryl groups such as (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 3- (N, N-diethylamino) phenyl group; (N, N-dimethylamino) methylphenyl group, (N, N-dialkylamino) alkylaryl group such as 4- [2- (N, N-dimethylamino) ethyl] phenyl group; Alkyl groups substituted with cyclic amino groups such as 1-pyrrolidinyl) propyl group, 3- (1-piperidinyl) propyl group, 3- (1-imidazolyl) propyl group; 4- (1-pyrrolidinyl) phenyl group, 4- Aryl groups substituted by cyclic amino groups such as (1-piperidinyl) phenyl group and 4- (1-imidazolyl) phenyl group; 4- [2- (1-pyrrolidinyl) ethyl] phenyl group, 4- [2- ( An alkylaryl group substituted with a cyclic amino group such as 1-piperidinyl) ethyl] phenyl group and 4- [2- (1-imidazolyl) ethyl] phenyl group can be given.

In the group formed by bonding a part of R ^{81 and} a part of R ⁸² or the group formed by bonding a part of any of R ⁸¹ and R ⁸² and a part of R ⁸⁴ , a nitrogen atom and The hydrocarbylene group optionally having an oxygen atom is a hydrocarbylene group or a hydrocarbylene group having a nitrogen atom and / or an oxygen atom.

Examples of the hydrocarbylene group include an alkylene group such as trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexane-1,6-diyl group; 1,4-phenylene And arylene groups such as a group. Examples of the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom include a group represented by —CH═N—CH═CH—, —CH═N—CH ₂ —CH ₂ — And a group represented by — (CH ₂ ) _t —O— (CH ₂ ) _u — (t and u are integers of 1 or more).

Examples of the divalent group represented by R ⁸³ include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom and / or an oxygen atom, a group formed by bonding a hydrocarbylene group and an oxygen atom, or hydrocarbylene. And a group formed by bonding a group represented by —NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom).

Examples of the hydrocarbylene group include an alkylene group, an alkenediyl group, an arylene group, and a group formed by bonding an arylene group and an alkylene group (hereinafter sometimes referred to as an arylene-alkylene group). Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and 2,2,4-trimethylhexane-1,6- A diyl group can be mentioned. Examples of the alkenediyl group include a pentane-2-ene-1,5-diyl group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the arylene-alkylene group include a phenylene-alkylene group, a naphthylene-alkylene group, and a biphenylene-alkylene group.

As the hydrocarbylene group having a nitrogen atom and / or an oxygen atom, for example, a group represented by —CH═N—CH═CH—, represented by —CH═N—CH ₂ —CH ₂ — And a group represented by — (CH ₂ ) _t —O— (CH ₂ ) _u — (t and u are integers of 1 or more). Examples of the group formed by bonding a hydrocarbylene group and an oxygen atom include a group represented by — (CH ₂ ) _u —O— (u is an integer of 1 or more).

Examples of the group formed by bonding a hydrocarbylene group and a group represented by —NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom) include, for example, — (CH ₂ ) v—NR—. And the like (R represents a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrogen atom, and v is an integer of 1 or more).

The compound represented by the above formula (8) is preferably a compound in which n is 0 and R ⁸⁴ represents an optionally substituted hydrocarbyl group or a hydrogen atom, that is, the following formula (8-1) A compound represented by the following formula: n is 0 and a part of R ^{81 and} a part of R ⁸⁴ are bonded together, or a hydrocarbylene group or a hydrocarbylene group and —NR ⁸⁵ —. A compound represented by a group formed by bonding to a group (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom), that is, a compound represented by the following formula (8-2); n is 1, and R ⁸³ is a hydro A compound representing a carbylene group, that is, a compound represented by the following formula (8-3); or n is 1, and R ⁸³ is a group formed by bonding a hydrocarbylene group and an oxygen atom, or a hydrocarbyl Ren group and ^{-NR 85} - group represented by ^{(R 85} Compound represents a hydrocarbyl group or a hydrogen atom) are bonded to made groups, i.e., a compound represented by the following formula (8-4).

Wherein ^(8-1), R ^{81, R 82} and ^{R 84} have the same meanings as ^R ^{81, R 82} and ^{R 84} in the formula (8).

Wherein ^{(8-2), R 82} has the same meaning as ^{R 82} in the formula (8). R ⁸⁶ represents a hydrocarbylene group or a group formed by bonding a hydrocarbylene group and a group represented by —NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom).

Wherein ^(8-3), R ^{81, R 82} and ^{R 84} have the same meanings as ^R ^{81, R 82} and ^{R 84} in the formula (8). R ⁸³ represents a hydrocarbylene group.

Wherein ^(8-4), R ^{81, R 82} and ^{R 84} have the same meanings as ^R ^{81, R 82} and ^{R 84} in the formula (8). R ⁸⁷ represents a hydrocarbylene group, A represents an oxygen atom or —NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom).

R ⁸¹ and R ⁸² in formula (8-1) each independently represent a hydrocarbyl group having 1 to 10 carbon atoms, or a part of R ^{81 and} a part of R ⁸² are bonded to each other. It preferably represents a hydrocarbylene group having 3 to 10 carbon atoms or a hydrocarbylene group having a nitrogen atom having 3 to 10 carbon atoms, each independently having 1 or more carbon atoms. Represents an alkyl group having 10 or less carbon atoms, or an aryl group having 6 to 10 carbon atoms, or an alkylene having 3 to 10 carbon atoms formed by bonding a part of R ^{81 and} a part of R ⁸² It is more preferable to represent a group, a group represented by —CH═N—CH═CH—, or a group represented by CH═N—CH ₂ —CH ₂ —, each independently having 1 or more carbon atoms 6 or less alkyl groups Is more preferable, and it is more preferable that each independently represents a methyl group or an ethyl group.

R ⁸⁴ in formula (8-1) preferably represents a hydrocarbyl group or a hydrogen atom, more preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrogen atom, more preferably 1 or more carbon atoms. More preferably, it represents an alkyl group of 6 or less, or a hydrogen atom, and more preferably represents a hydrogen atom, a methyl group, or an ethyl group.

Among the compounds represented by formula (8-1), examples of the compound in which R ⁸⁴ represents a hydrocarbyl group include N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-ethylacetamide and the like. N, N-dihydrocarbylacetamide; N, N-dihydrocarbylacrylamide such as N-dimethylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide; N, N-dimethylmethacrylamide, N, N And N, N-dihydrocarbyl methacrylamide such as -diethylmethacrylamide and N-methyl-N-ethylmethacrylamide.

Of the compounds represented by formula (8-1), examples of the compound in which R ⁸⁴ represents a hydrogen atom include N, N-dimethylformamide, N, N-diethylformamide, N-methyl-N-ethylformamide and the like. Of N, N-dihydrocarbylformamide.

In formula (8-2), examples of the hydrocarbylene group for R ⁸⁶ include an alkylene group, an alkenediyl group, an arylene group, and a group formed by bonding an arylene group to an alkylene group (hereinafter referred to as an arylene-alkylene group). And the like. As the alkylene group, an alkylene group having 1 to 12 carbon atoms is preferable. For example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, 2, Examples include 2,4-trimethylhexane-1,6-diyl group. As the alkenediyl group, an alkenediyl group having 4 to 12 carbon atoms is preferable, and examples thereof include a pentane-2-ene-1,5-diyl group. The arylene group includes 6 to 12 carbon atoms. An arylene group is preferable, and examples thereof include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the arylene-alkylene group include a phenylene-alkylene group, a naphthylene-alkylene group, and a biphenylene-alkylene group. Examples of the group formed by bonding a hydrocarbylene group in R ⁸⁶ and a group represented by —NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom) include — (CH ₂ ) _v —NR A group represented by-(R represents a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrogen atom, and v is an integer of 1 or more).

R ⁸² in formula (8-2) preferably represents a hydrocarbyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. More preferably, an alkyl group having 1 to 6 carbon atoms or a phenyl group is more preferable, and a methyl group, an ethyl group or a phenyl group is still more preferable.

R ⁸⁶ in formula (8-2) is a hydrocarbylene group having 1 to 10 carbon atoms, or a hydrocarbylene group having 1 to 10 carbon atoms and a group represented by —NR ⁸⁸ — ( R ⁸⁸ preferably represents a group formed by bonding to a hydrocarbyl group having 1 to 10 carbon atoms or a hydrogen atom, and is an alkylene group having 3 to 6 carbon atoms, or — (CH ₂ ) More preferably a group represented by _w —NR— (R represents a hydrocarbyl group having 1 to 10 carbon atoms, and w is an integer of 2 to 5). More preferably, it represents a methylene group, a pentamethylene group, or a group represented by — (CH ₂ ) ₂ —N (CH ₃ ) —.

Of the compounds represented by the formula (8-2), examples of the compound in which R ⁸⁶ represents a hydrocarbylene group include N-methyl-β-propiolactam, N-phenyl-β-propiolactam and the like. N-hydrocarbyl-β-propiolactam; N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-methyl-5 N-hydrocarbyl-2-pyrrolidone such as methyl-2-pyrrolidone; N-hydrocarbyl-2-piperidone such as N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2-piperidone; N- N-hydrocarbyl-ε-caprolactam such as methyl-ε-caprolactam and N-phenyl-ε-caprolactam; N-methyl-ω-laurylacta , It may be mentioned N- hydrocarbyl -ω- Lau Lilo lactams such N- vinyl -ω- Lau Lilo lactam. Of these, N-methyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-methyl-ε-caprolactam and N-phenyl-ε-caprolactam are preferable, and N-phenyl-2- more preferable. Pyrrolidone, N-methyl-ε-caprolactam.

Among the compounds represented by the formula (8-2), R ⁸⁶ represents a group formed by bonding a hydrocarbylene group and a group represented by —NR ⁸⁵ — (R ⁸⁵ is a hydrocarbyl group or a hydrogen atom). Examples of the compound include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-divinyl-2-imidazolidinone, 1-methyl-3-ethyl- Mention may be made of 1,3-dihydrocarbyl-2-imidazolidinone such as 2-imidazolidinone. Of these, 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone are preferred, and 1,3-dimethyl-2-imidazolidinone is more preferred.

R ⁸³ in formula (8-3) preferably represents a hydrocarbylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms. It preferably represents an arylene group, more preferably represents an alkylene group having 1 to 6 carbon atoms or a phenylene group, and more preferably represents an ethylene group, a trimethylene group or a 1,4-phenylene group.

R ⁸⁴ in formula (8-3) preferably represents a hydrocarbyl group having 1 to 10 carbon atoms or a hydrocarbyl group having 3 to 10 carbon atoms substituted with a dialkylamino group. It more preferably represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a dialkylaminoalkyl group having 3 to 6 carbon atoms, or a dialkylaminoaryl group having 8 to 10 carbon atoms. Preferably, a methyl group, an ethyl group, a dialkylaminomethyl group having 3 to 6 carbon atoms, a dialkylaminoethyl group having 4 to 6 carbon atoms, a phenyl group, or a dialkylaminophenyl group having 8 to 10 carbon atoms Is more preferable.

R ⁸¹ and R ⁸² in formula (8-3) each independently represent a hydrocarbyl group having 1 to 10 carbon atoms, or a part of R ^{81 and} a part of R ⁸² are bonded to each other. It preferably represents a hydrocarbylene group having 3 to 10 carbon atoms or a hydrocarbylene group having a nitrogen atom having 3 to 10 carbon atoms, each independently having 1 or more carbon atoms. Represents an alkyl group having 10 or less carbon atoms, or an aryl group having 6 to 10 carbon atoms, or a group in which R ⁸¹ is bonded to R ⁸² and R ⁸¹ is bonded to R ^82. An alkylene group of 10 or less, a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, or — (CH ₂ ) ₂ —O— (CH It represents a group represented by - ₂₎ ₂ Preparative more preferably, each independently represent an alkyl group having 1 to 6 carbon atoms, or formed by combining a portion of a portion R ⁸² of R ^81, having three or more carbon atoms 6 It is more preferable to represent the following alkylene group, a group represented by —CH═N—CH═CH—, or a group represented by —CH═N—CH ₂ —CH ₂ —, and each independently represents methyl Represents a group or an ethyl group, or a tetramethylene group, a hexamethylene group, or a group represented by —CH═N—CH═CH—, which is formed by bonding a part of R ^{81 and} a part of R ⁸² More preferably.

Among the compounds represented by formula (8-3), examples of the compound in which R ⁸³ represents an arylene group and R ⁸⁴ represents an alkyl group include 4- (N, N-dimethylamino) acetophenone, 4- ( 4- (N, N-dihydrocarbylamino) acetophenone such as N-methyl-N-ethylamino) acetophenone, 4- (N, N-diethylamino) acetophenone; 4 such as 4 ′-(imidazol-1-yl) acetophenone -Cyclic aminoacetophenone compounds can be mentioned. Of these, 4-cyclic aminoacetophenone compounds are preferable, and 4 ′-(imidazol-1-yl) acetophenone is more preferable.

Among the compounds represented by formula (8-3), examples of the compound in which R ⁸³ represents a hydrocarbylene group and R ⁸⁴ represents a hydrocarbyl group or a substituted hydrocarbyl group include 1,7-bis (methylethylamino) ) -4-heptanone, bis (dihydrocarbylaminoalkyl) ketones such as 1,3-bis (diphenylamino) -2-propanone. Examples of the compound in which R ⁸³ represents an arylene group and R ⁸⁴ represents an aryl group or a substituted aryl group include 4-N, N-dimethylaminobenzophenone, 4-N, N-diethylaminobenzophenone, 4-N, N— 4- (dihydrocarbylamino) benzophenone such as di-t-butylaminobenzophenone, 4-N, N-diphenylaminobenzophenone; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone 4,4′-bis (dihydrocarbylamino) benzophenone such as 4,4′-bis (diphenylamino) benzophenone. Among these, 1,7-bis (methylethylamino) -4-heptanone, 4-N, N-dimethylaminobenzophenone, 4-N, N-diethylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone 4,4′-bis (diethylamino) benzophenone, 4-N, N-dimethylaminobenzophenone, 4-N, N-diethylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bis (diethylamino) benzophenone is more preferred.

In formula (8-4), the oxygen atom or NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbyl group or a hydrogen atom) in A represents an oxygen atom or —NR— (R represents a carbon atom number of 1 to 5). Preferably represents a hydrocarbylene group or a hydrogen atom), more preferably represents an oxygen atom or a group represented by —NH—, and represents a group represented by —NH—. More preferably, it represents.

In formula (8-4), examples of the hydrocarbylene group represented by R ⁸⁷ include an alkylene group, an alkenediyl group, an arylene group, and a group formed by bonding an arylene group and an alkylene group (hereinafter referred to as an arylene-alkylene group). May be called.). The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms. For example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and 2, A 2,4-trimethylhexane-1,6-diyl group can be mentioned. The alkenediyl group is preferably an alkenediyl group having 4 to 12 carbon atoms, and examples thereof include a pentane-2-ene-1,5-diyl group. As the arylene group, an arylene group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the arylene-alkylene group include a phenylene-alkylene group, a naphthylene-alkylene group, and a biphenylene-alkylene group.

R ⁸⁴ in formula (8-4) preferably represents a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, a vinyl group, More preferably, it represents a propenyl group, and more preferably a vinyl group.

R ⁸⁷ in formula (8-4) preferably represents a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an ethylene group or More preferably, it represents a trimethylene group, and more preferably a trimethylene group.

R ⁸¹ and R ⁸² in formula (8-4) each independently represent a hydrocarbyl group having 1 to 10 carbon atoms, or a part of R ^{81 and} a part of R ⁸² are bonded to each other. It preferably represents a hydrocarbylene group having 3 to 10 carbon atoms or a hydrocarbylene group having a nitrogen atom having 3 to 10 carbon atoms, each independently having 1 or more carbon atoms. Represents an alkyl group having 10 or less carbon atoms, or an aryl group having 6 to 10 carbon atoms, or an alkylene having 3 to 10 carbon atoms formed by bonding a part of R ^{81 and} a part of R ⁸² A group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, or — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ — It is more preferable to represent the group represented by Each independently represent an alkyl group having 1 to 6 carbon atoms, or formed by combining a portion of a portion R ⁸² of R ^81, an alkylene group having 3 to 6 carbon atoms More preferably a group represented by —CH═N—CH═CH— or a group represented by —CH═N—CH ₂ —CH ₂ —, each independently a methyl group or ethyl Represents a tetramethylene group, a hexamethylene group, or a group represented by —CH═N—CH═CH—, which is formed by bonding a part of R ^{81 and} a part of R ^82. Even more preferred.

Among the compounds represented by formula (8-4), examples of the compound in which A represents an oxygen atom include 2- (dihydrocarbylamino) such as 2- (dimethylamino) ethyl acrylate and 2- (diethylamino) ethyl acrylate. ) Ethyl acrylate; 3- (dihydrocarbylamino) propyl acrylate such as 3- (dimethylamino) propyl acrylate; 2- (dihydrocarbylamino) ethyl such as 2- (dimethylamino) ethyl methacrylate and 2- (diethylamino) ethyl methacrylate Methacrylate; 3- (Dihydrocarbylamino) propyl methacrylate such as 3- (dimethylamino) propyl methacrylate can be mentioned. Of these, 2- (dimethylamino) ethyl acrylate, 3- (dimethylamino) propyl acrylate, 2- (dimethylamino) ethyl methacrylate, and 3- (dimethylamino) propyl methacrylate are preferred, and 2- (dimethylamino) ethyl is preferred. An acrylate, 3- (dimethylamino) propyl acrylate is more preferable.

Of the compounds represented by the formula (8-4), examples of the compound in which A represents a group represented by —NR ⁸⁵ — (R ⁸⁵ represents a hydrocarbylene group or a hydrogen atom) include N— ( N- (2-dihydrocarbylaminoethyl) acrylamide such as 2-dimethylaminoethyl) acrylamide, N- (2-diethylaminoethyl) acrylamide; N- (3-dimethylaminopropyl) acrylamide, N- (3-diethylaminopropyl) N- (3-dihydrocarbylaminopropyl) acrylamide such as acrylamide; N- (4-dihydrocarbylaminobutyl) acrylamide such as N- (4-dimethylaminobutyl) acrylamide, N- (4-diethylaminobutyl) acrylamide; N -(2-Dimethylaminoethyl) methacrylamide, N- N- (2-dihydrocarbylaminoethyl) methacrylamide such as 2-diethylaminoethyl) methacrylamide; N- (3 such as N- (3-dimethylaminopropyl) methacrylamide, N- (3-diethylaminopropyl) methacrylamide -Dihydrocarbylaminopropyl) methacrylamide; N- (4-dihydrocarbylaminobutyl) methacrylamide such as N- (4-dimethylaminobutyl) methacrylamide and N- (4-diethylaminobutyl) methacrylamide . Among these, N- (2-dimethylaminoethyl) acrylamide, N- (3-dimethylaminopropyl) acrylamide, and N- (4-dimethylaminobutyl) acrylamide are preferable, and N- (2-dimethylaminoethyl) acrylamide is preferable. N- (3-dimethylaminopropyl) acrylamide is more preferable.

The preparation of the conjugated diene polymer includes an agent for adjusting the vinyl bond amount of the monomer unit derived from the conjugated diene compound, a monomer unit derived from the conjugated diene compound in the conjugated diene polymer chain, and an aroma. May be performed in the presence of an agent that adjusts the distribution of monomer units derived from the group vinyl compound and the monomer units derived from other compounds (hereinafter collectively referred to as “adjusting agent”). .

As the regulator, ether compounds, tertiary amines, phosphine compounds, alkali metal alkoxides, alkali metal phenoxides, and the like can be used. Examples of the ether compound include cyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and 2,2-di (tetrahydrofuryl) propane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, Aliphatic diethers such as ethylene glycol diethyl ether and ethylene glycol dibutyl ether; Aliphatic triethers such as diethylene glycol diethyl ether and diethylene glycol dibutyl ether; Aromatics such as diphenyl ether, anisole, 1,2-dimethoxybenzene and 3,4-dimethoxytoluene Ether. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, 1,1,2,2-tetramethylethylenediamine, N, N-diethylaniline, pyridine and quinoline. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, and triphenylphosphine. 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. You may use these individually or in combination of 2 or more types.

When producing the conjugated diene polymer according to the present embodiment, a coupling agent may be added to the polymerization solution from the start of polymerization of the monomer to the termination of polymerization. Examples of the coupling agent include compounds represented by the above formula (5) or (6).

Examples of coupling agents include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, methyltrimethoxysilane, dimethoxydimethyl. Examples include silane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.

The addition amount of the coupling agent is not particularly limited, but when the polymerization initiator contains an alkali metal, in order to improve the cold flow resistance of the conjugated diene polymer to be produced, preferably 0.03 mol per 1 mol of the alkali metal. It is above, More preferably, it is 0.05 mol or more. Further, the amount of the coupling agent added is preferably 0.4 mol or less, more preferably 0.3 mol or less, per 1 mol of the alkali metal in order to improve the fuel economy of the modified conjugated diene polymer composition. .

[Method for producing conjugated diene polymer composition]
The method for producing a conjugated diene polymer composition of the present embodiment includes a step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene polymer, and a conjugated diene polymer. And a step of mixing a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group.

In the terminal and / or molecular chain of the conjugated diene polymer, a unit based on a compound having a hetero atom and / or a silicon atom as a modifier may be introduced. When a unit based on a modifier is introduced into the molecular chain of a polymer, a compound having a functional group copolymerizable with a conjugated diene compound as a compound having a hetero atom and / or a silicon atom (for example, the formula (7) Can be used as a monomer. That is, a conjugated diene polymer is obtained by copolymerizing a monomer containing a conjugated diene compound and a compound having a functional group copolymerizable with the conjugated diene compound in a hydrocarbon solvent in the presence of a polymerization initiator. Obtainable.

When the unit based on the modifier is introduced into the terminal of the conjugated diene polymer, the compound having a functional group capable of reacting with the active terminal of the polymer (for example, the formula ( The compound represented by 6) or (8) can be used. In this case, the conjugated diene polymer may be produced by the following method.

First, a monomer containing a conjugated diene compound is polymerized in a hydrocarbon solvent in the presence of a polymerization initiator to obtain a polymer having an active terminal. Next, this polymer is reacted with a compound having a functional group capable of reacting with the active terminal of the polymer to introduce a unit based on a modifier at the terminal of the polymer.

That is, the method for producing a conjugated diene polymer composition of the present embodiment includes a step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene polymer, and a conjugated diene polymer composition. Reacting a compound with a compound having a hetero atom and / or a silicon atom to obtain a terminal-modified conjugated diene polymer, a terminal-modified conjugated diene polymer, a carbonyl group and the carbonyl group; And a step of mixing with a compound having a functional group capable of forming a hydrogen bond.

Further, a compound having a functional group copolymerizable with a conjugated diene compound and a compound having a functional group capable of reacting with the active terminal of the polymer are used in combination, and based on a modifier in the molecular chain and at the terminal of the polymer. Units may be introduced.

Conjugated diene polymers can be recovered by known recovery methods, for example, adding a coagulant to a hydrocarbon solution of a conjugated diene polymer, blowing steam into the hydrocarbon solution of a conjugated diene polymer, and gasifying volatile components. For example, a method of removing by steam (steam stripping), a method of concentrating in a flushing tank and further devolatilizing with a vent extruder or the like, and a method of devolatilizing directly with a drum dryer or the like. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

In the present embodiment, in order to improve the processability of the conjugated diene polymer, before separating the solvent, if necessary, the extending oil is mixed into the diene polymer solution, and the conjugated diene polymer is converted into the oil. It can be recovered as an extended rubber.

The method of mixing the conjugated diene polymer with a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group is not particularly limited. For example, a method of dissolving the compound in a solvent and mixing it with a conjugated diene polymer solution, a method of melting the compound and mixing it with a conjugated diene polymer solution, and a method of kneading the compound and the conjugated diene polymer It is possible to take a technique such as

A reinforcing material may be added to the polymer composition according to this embodiment. Examples of the reinforcing material include silica, calcium silicate, aluminum silicate, aluminum hydroxide, and carbon black. You may use a reinforcing material individually or in combination of 2 or more types.

Examples of silica include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, and precipitated silica. The BET specific surface area of silica is preferably 50 m ² / g to 250 m ² / g. The BET specific surface area is measured according to ASTM D1993-03. As commercial products of silica, trade names “Ultrasil VN3GR”, “Ultrasil 5000GR”, “Ultrasil 7000GR”, “Ultrasil 9100GR” manufactured by Evonik, and “VN3”, “trade names” manufactured by Tosoh Silica “AQ”, “ER”, “RS-150”, trade names “Zeosil 1115MP”, “Zeosil 1165MP” manufactured by Solvay, Inc. can be used. Silica may be used alone or in combination of two or more.

Examples of carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Examples of channel black include EPC, MPC, and CC. Examples of the furnace carbon black include SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF, and ECF. Examples of the thermal black include FT and MT. Carbon blacks may be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 m ² / g to 200 m ² / g. The amount of dibutyl phthalate (DBP) absorbed by carbon black is preferably 5 mL / 100 g to 300 mL / 100 g. The nitrogen adsorption specific surface area can be measured according to ASTM D4820-93, and the DBP absorption amount can be measured according to ASTM D2414-93. Commercially available carbon black products include “Dia Black N339” manufactured by Mitsubishi Chemical Corporation, “Seast 6”, “Seast 7HM”, “Seast KH” manufactured by Tokai Carbon Co., Ltd., Orion Engineered Carbons The product names “CK 3”, “Special Black 4A”, etc. can be used.

The content of the reinforcing material in the polymer composition is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the polymer. Further, the blending amount is more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, in order to increase wear resistance and strength. Further, the content of the reinforcing material is more preferably 120 parts by mass or less, and still more preferably 100 parts by mass or less, in order to enhance the reinforcement.

Other polymer components, additives and the like may be further blended in the polymer composition according to the present embodiment.

Examples of other polymer components include conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, butyl rubber, natural rubber, ethylene-propylene copolymer, and ethylene-octene copolymer. Can be mentioned. These polymer components may be used alone or in combination of two or more.

In the case where other polymer components are blended, the content of the polymer according to this embodiment in the polymer composition is the total amount of polymer components (including conjugated diene polymers) from the viewpoint of improving wet grip performance. Preferably it is 10 mass parts or more with respect to a mass part, More preferably, it is 20 mass parts 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 di-tert-butyl peroxide; calcium carbonate, talc, alumina, clay, hydroxylation Examples include fillers such as aluminum 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 mass, more preferably 0.3 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component. Part.

Examples of the vulcanization accelerator include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethyl Thiuram vulcanization accelerators such as thiuram disulfide; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, Sulfenamide vulcanization accelerators such as N-oxyethylene-2-benzothiazole sulfenamide and N, N′-diisopropyl-2-benzothiazole sulfenamide; Include guanidine-based vulcanization accelerator. Vulcanization accelerators may be used alone or in combination of two or more. The blending amount of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the polymer component.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxy. Silane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (tri Ethoxysil ) Propyl) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide and .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide and the like. You may use a silane coupling agent individually or in combination of 2 or more types. As commercial products, trade names “NXT Silane”, “NXT-Z30”, “NXT-Z45” and “NXT-Z30”, “product names“ Si69 ”,“ Si75 ”,“ Si266 ”, etc. manufactured by Evonik, etc., such as Momentive Performance Materials, Inc. NXT-Z60 "," NXT-Z100 ", etc. can be used.

The compounding amount of the silane coupling agent is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of the reinforcing material.

Examples of the extending oil include aromatic mineral oil (viscosity specific gravity constant (VGC value) 0.900 to 1.049), naphthenic mineral oil (VGC value 0.850). To 0.899) and paraffinic mineral oil (VGC value 0.790 to 0.849). The polycyclic aromatic content of the extender oil is preferably less than 3% by mass, more preferably less than 1% by mass. The polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method. The aromatic compound content (CA) of the extender oil is preferably 20% by mass or more. The extension oils may be used alone or in combination of two or more.

As a method for producing the polymer composition according to this embodiment, a method of kneading each component with a known mixer such as a roll or a Banbury mixer is preferable.

As the kneading conditions, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 to 200 ° C., preferably 80 to 190 ° C., and the kneading time is usually 30 seconds. -30 minutes, and preferably 1-30 minutes. When a vulcanizing agent and a vulcanization accelerator are blended, 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 being subjected to a vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

The polymer composition according to the present embodiment can sufficiently suppress cold flow, and is used for tires, shoe soles, flooring materials, vibration-proof materials, and the like, and is particularly preferably used for tires.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Physical property evaluation was performed by the following method.

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

2. Styrene unit content (unit: mass%)
According to JIS K6383 (1995), the content of monomer units derived from styrene of the polymer was determined from the refractive index.
3. Weight average molecular weight (Mw)
Mw of the conjugated diene polymer was measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8).
(1) Equipment: HLC-8220 manufactured by Tosoh Corporation
(2) Separation column: TSKgel SuperHM-H manufactured by Tosoh Corporation (two in series)
(3) Measurement temperature: 40 ° C
(4) Carrier: Tetrahydrofuran (5) Flow rate: 0.6 mL / min (6) Injection volume: 5 μL
(7) Detector: Differential refraction (8) Molecular weight standard: Standard polystyrene

4). Cold Flow Test The polymer composition was press-molded at 100 ° C. for 20 minutes to produce a cylindrical test piece having a diameter of 29 mm and a height of 25 mm. The test piece was stored in an oven heated to 40 ° C., the height of the test piece after 4 days was measured, and the height retention rate was determined by the following formula.
Height retention ratio (%) = (Test piece height after 4 days / Test piece height before test) × 100

[Example 1]
(Conjugated diene polymer)
A stainless polymerization reactor with an internal volume of 5 L and equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, industrial hexane (manufactured by Sumitomo Chemical Co., Ltd., trade name: hexane (general product), density 0.68 g / mL) 2.55 kg, 1,3-butadiene 135 g, styrene 45 g, tetrahydrofuran 1.5 mL and ethylene glycol diethyl 1.2 mL of ether was charged into the polymerization reactor. Next, an n-hexane solution containing 2.39 mmol of n-butyllithium (n-BuLi) was charged into the polymerization reactor to initiate 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 1,3-butadiene and styrene are continuously fed into the polymerization reactor while performing a polymerization reaction. For 2.5 hours. The amount of 1,3-butadiene supplied was 202.5 g, and the amount of styrene supplied was 67.5 g. Next, 20 mL of a hexane solution containing 0.15 mL of methanol was added to the obtained polymerization solution, and the polymerization solution was further stirred for 5 minutes.

A polymer obtained by extracting the stirred product from the polymerization reactor, drying a part of the stirred product for 12 hours at room temperature, evaporating most of the volatile components, and further drying under reduced pressure at 65 ° C. for 6.5 hours. The vinyl bond content, styrene unit content and Mw were measured.

To the stirred product, 1.8 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) And 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) were added to obtain a solution containing a conjugated diene polymer.

(Polymer composition)
A solution containing 50 g of a conjugated diene polymer and 0.5 g of 12-hydroxystearic acid (hereinafter abbreviated as “12HSA”) as a cold flow inhibitor and 50 mL of tetrahydrofuran was added at room temperature to 12 g. After drying for a time, it was dried under reduced pressure at 65 ° C. for 6.5 hours to prepare a polymer composition.

[Comparative Example 1]
A polymer composition was prepared in the same manner as in Example 1 except that 12HSA was not added.

[Comparative Example 2]
A polymer composition was prepared in the same manner as in Example 1 except that 0.5 g of 2,2′-bipyridyl was added instead of 12HSA.

Table 1 shows the vinyl bond content, styrene unit content and Mw of the polymers in Example 1 and Comparative Examples 1 and 2, the type of cold flow inhibitor added to the polymer composition, and the results of the cold flow test. Shown in

[Example 2]
(Conjugated diene polymer)
A stainless polymerization reactor with an internal volume of 5 L and equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 2.55 kg of “hexane (general product)”, 135 g of 1,3-butadiene, 45 g of styrene, 1.5 mL of tetrahydrofuran, and 1.2 mL of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-hexane solution containing 1.67 mmol of bis (diethylamino) methylvinylsilane and 2.39 mmol of n-BuLi was charged into the polymerization reactor to initiate 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 1,3-butadiene and styrene are continuously fed into the polymerization reactor while performing a polymerization reaction. For 2.5 hours. The amount of 1,3-butadiene supplied was 202.5 g, and the amount of styrene supplied was 67.5 g.

Next, the obtained polymerization solution was stirred at a stirring speed of 130 rpm, 2.39 mmol of N- (3-dimethylaminopropyl) acrylamide was added and stirred for 15 minutes, and then 20 mL of a hexane solution containing 0.15 mL of methanol was added. In addition, the polymerization solution was stirred for an additional 5 minutes.

The stirred product in the polymerization reactor was withdrawn, a part of the stirred product was dried at room temperature for 12 hours, most of the volatile components were evaporated, and further dried under reduced pressure at 65 ° C. for 6.5 hours. The vinyl bond content, styrene unit content and Mw of the coalesced were measured.

To the agitation, 1.8 g of “Sumilyzer GM” and 0.9 g of “Sumilyzer TP-D” were added to obtain a solution containing a conjugated diene polymer.

(Polymer composition)
A solution obtained by adding 0.5 g of 12HSA and 50 mL of tetrahydrofuran to a solution containing 50 g of a conjugated diene polymer was dried at room temperature for 12 hours, and then dried under reduced pressure at 65 ° C. for 6.5 hours to obtain a polymer composition. Produced.

[Example 3]
A polymer composition was prepared in the same manner as in Example 2, except that 0.5 g of 2-hydroxycaprylic acid (hereinafter abbreviated as “2HOA”) was added instead of 12HSA.

[Example 4]
A polymer was obtained in the same manner as in Example 2 except that 0.5 g of N-lauroyl-L-glutamic acid-α, γ-dibutyramide (hereinafter abbreviated as “LGBA”) was added instead of 12HSA. A composition was prepared.

[Comparative Example 3]
A polymer composition was prepared in the same manner as in Example 2 except that 0.5 g of 12HSA was not added.

[Comparative Example 4]
A polymer composition was prepared in the same manner as in Example 2 except that 0.5 g of 3-amino-1,2,4-triazole (hereinafter abbreviated as “triazole”) was added instead of 12HSA. Produced.

The vinyl bond content of the polymers in Examples 2 to 4 and Comparative Examples 3 and 4, the content and Mw of styrene units, the type of cold flow inhibitor added to the polymer composition, and the results of the cold flow test. It shows in Table 2.

[Example 5]
(Conjugated diene polymer)
A stainless polymerization reactor with an internal volume of 20 L equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of “hexane (general product)”, 720 g of 1,3-butadiene, 80 g of styrene, 6.07 mL of tetrahydrofuran and 0.75 mL of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-hexane solution containing 28.57 mmol of n-BuLi was charged into the polymerization reactor to initiate 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 1,3-butadiene and styrene are continuously fed into the polymerization reactor while performing a polymerization reaction. For 2.5 hours. The amount of 1,3-butadiene supplied was 1080 g, and the amount of styrene supplied was 120 g.

Next, the obtained polymerization solution was stirred at a stirring speed of 130 rpm, 28.57 mmol of [3- (diethylamino) propyl] trimethoxysilane was added and stirred for 15 minutes, and then 20 mL of a hexane solution containing 1.74 mL of methanol. And the polymerization solution was stirred for another 5 minutes.

To the agitation, 8.0 g of “Sumilyzer GM” and 4.0 g of “Sumilyzer TP-D” were added to obtain a solution containing a conjugated diene polymer.

(Polymer composition)
To a solution containing 100 g of a conjugated diene polymer, 1.0 g of 12HSA and 100 mL of tetrahydrofuran were added, and the mixture was dried at room temperature for 12 hours and then dried under reduced pressure at 65 ° C. for 6.5 hours to produce a polymer composition. did.

[Comparative Example 5]
A polymer composition was prepared in the same manner as in Example 5 except that 12HSA was not added.

Table 3 shows the vinyl bond content, styrene unit content and Mw of the polymer in Example 5 and Comparative Example 5, the type of cold flow inhibitor added to the polymer composition, and the results of the cold flow test. .

Claims

A conjugated diene polymer having a weight average molecular weight of 80000 or more;
A compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group;
A conjugated diene polymer composition comprising:
2. The conjugated diene polymer composition according to claim 1, wherein the functional group is a group represented by —OH or —NH—.
The conjugated diene polymer composition according to claim 1 or 2, wherein the compound is an aliphatic hydroxycarboxylic acid compound or an aliphatic amide compound having two or more amide groups.
The conjugated diene polymer composition according to any one of claims 1 to 3, wherein the compound is a linear aliphatic hydroxycarboxylic acid compound or an aliphatic amide compound having 3 to 6 amide groups. object.
A step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene polymer;
Mixing the conjugated diene polymer with a compound having a carbonyl group and a functional group capable of forming a hydrogen bond with the carbonyl group;
A process for producing a conjugated diene polymer composition.
A step of reacting a monomer containing a conjugated diene compound in a hydrocarbon solvent to obtain a conjugated diene polymer;
Reacting the conjugated diene polymer with a compound having a hetero atom and / or a silicon atom to obtain a terminal-modified conjugated diene polymer;
Mixing the terminal-modified conjugated diene polymer with a carbonyl group and a compound having a functional group capable of forming a hydrogen bond with the carbonyl group;
A process for producing a conjugated diene polymer composition.
The method according to claim 5 or 6, wherein the monomer further comprises a compound having a hetero atom and / or a silicon atom.
The method according to any one of claims 5 to 7, wherein the functional group is a group represented by -OH or -NH-.
The method according to any one of claims 5 to 8, wherein the compound is an aliphatic hydroxycarboxylic acid compound or an aliphatic amide compound having two or more amide groups.