JP2017210543A - Method for producing conjugated diene-based polymer, method for producing conjugated diene-based polymer composition, method for producing rubber composition, and method for producing tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a conjugated diene-based polymer capable of stably and easily producing a conjugated diene-based polymer which has high randomness and hardly forms a structural unit of a block vinyl aromatic compound.SOLUTION: A method for producing a conjugated diene-based polymer including a vinyl aromatic compound unit and a conjugated diene compound unit includes the following steps 1 to 3. (Step 1) a step of adding 50 wt.% or more the vinyl aromatic compound with the total amount of a vinyl aromatic compound used in polymerization and less than 90% of the conjugated diene compound with respect to the total amount of the conjugated diene compound used in polymerization compound to a reactor. (Step 2) a step of adding a polymerization initiator to the reactor after or simultaneously with the step 1 to polymerize the vinyl aromatic compound and the conjugated diene-based compound prepared in the reactor. (Step 3) a step of continuously adding a residue of the vinyl aromatic compound and the conjugated diene compound to the reactor, after the step 2.SELECTED DRAWING: None

Description

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

  Conventionally, from the viewpoint of strength when forming a tire, it is preferable that the tire composition has higher randomness in the copolymer chain contained in the composition. Further, if the copolymer chain contains a structural unit derived from a block vinyl aromatic compound in a predetermined amount or more (for example, 5% by mass or more), the strength when made into a tire may be relatively lowered. Are known.

  For example, in Patent Document 1, high styrene and low vinyl SSBR are added by adding the total amount of styrene and butadiene of less than 60% by mass to the reactor, and adding the butadiene residue in two portions after the start of the reaction. Disclosed is a styrene-butadiene polymer having a styrene gradient at the center and terminal in a polymer chain to be polymerized and a method for producing the same.

International Publication No. 2009/134665

  However, the polymer obtained by the conventional production method expresses excellent wet grip performance when it has a structural unit of a high content of vinyl aromatic compound and a low content of vinyl bond, but is used for polymerization. Randomness tends to decrease due to the influence of the copolymer properties of the monomer. Therefore, it is difficult to obtain a polymer having high randomness and having a high content vinyl aromatic compound structural unit and a low content vinyl bond. Further, the polymer obtained by the production method described in Patent Document 1 is still insufficient in randomness, and the structural unit of the block vinyl aromatic compound is relatively easily formed.

  Therefore, the present invention provides a conjugated diene polymer that can stably and easily produce a conjugated diene polymer that has high randomness and is difficult to form a structural unit of a block vinyl aromatic compound. An object is to provide a manufacturing method.

That is, the present invention includes the following aspects.
[1]
A method for producing a conjugated diene polymer comprising a vinyl aromatic compound unit and a conjugated diene compound unit,
Having the following steps 1 to 3,
A method for producing a conjugated diene polymer.
(Step 1) The total amount of the vinyl aromatic compound used in the polymerization is 50% by mass or more, and the total amount of the conjugated diene compound used in the polymerization is less than 90% by mass. Step of adding the conjugated diene compound to the reactor (Step 2) After or simultaneously with Step 1, a polymerization initiator is added to the reactor, and the vinyl aromatic compound and the conjugated diene prepared in the reactor are added. Step of polymerizing system compound (Step 3) Step of continuously adding the remainder of the vinyl aromatic compound and the conjugated diene compound to the reactor after Step 2 [2]
The step 1 is a step of preparing 100% by mass of the vinyl aromatic compound in the reactor with respect to the total amount of the vinyl aromatic compound used for polymerization.
The method for producing a conjugated diene polymer according to [1].
[3]
In the step 3, the time for continuously adding the vinyl aromatic compound and the residue of the conjugated diene compound is 0.2 minutes or more and less than 120 minutes,
[1] The method for producing a conjugated diene polymer according to [2].
[4]
Step 1 is a step of further adding a compound having an ether group or an amino group to the reactor.
[1] A method for producing a conjugated diene polymer according to any one of [3].
[5]
The compound is a compound having an ether group, and is a compound represented by the following general formula (A).
[1] A method for producing a conjugated diene polymer according to any one of [4].
(In the formula, R _{1 to} R ₄ each independently represents a functional group formed by combining one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, and an oxygen atom. Show.)
[6]
After the step 3, further comprising adding a coupling agent to the reactor;
[1] A method for producing a conjugated diene polymer according to any one of [5].
[7]
The coupling agent is a compound having one or more selected from the group consisting of an alkoxide group, an epoxy group, an ester group, and a halogen group.
[6] The method for producing a conjugated diene polymer according to [6].
[8]
The total amount of the vinyl aromatic compound is 30% by mass or more and 65% by mass or less with respect to the total amount of the vinyl aromatic compound and the total amount of the conjugated diene compound used for polymerization.
[1] A method for producing a conjugated diene polymer according to any one of [7].
[9]
The polymerization conversion rate of the vinyl aromatic compound is 93% or more.
[1] A method for producing a conjugated diene polymer according to any one of [8].
[10]
The content of the block vinyl aromatic compound in the conjugated diene polymer is 0.5% by mass or more and less than 3.5% by mass.
[1] A method for producing a conjugated diene polymer according to any one of [9].
[11]
The 1,2-vinyl bond content in the conjugated diene polymer is 10% by mass or more and 40% by mass or less.
[1] A method for producing a conjugated diene polymer according to any one of [10].
[12]
The rubber component containing the conjugated diene polymer obtained by the production method according to any one of [1] to [11], and 0.5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the rubber component. A step of mixing a silica-based inorganic filler,
The rubber component contains the conjugated diene polymer in an amount of 20% by mass or more based on the total amount of the rubber component.
A method for producing a conjugated diene polymer composition.
[13]
The method further comprises a step of crosslinking the conjugated diene polymer composition obtained by the production method according to [12].
A method for producing a rubber composition.
[14]
Having a step of molding a tire containing the rubber composition obtained by the production method according to [13].
Tire manufacturing method.

  According to the method for producing a conjugated diene polymer according to the present invention, it is possible to stably and easily produce a conjugated diene polymer that has high randomness and is difficult to form a structural unit of a block vinyl aromatic compound. it can.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not restrict | limited to the following this embodiment, A various deformation | transformation can be implemented within the range of the summary.

[Method for producing conjugated diene polymer]
The manufacturing method of the conjugated diene polymer of this embodiment is a manufacturing method of the conjugated diene polymer containing a vinyl aromatic compound unit and a conjugated diene compound unit. Moreover, it has the following processes 1-3.
(Step 1) 50% by mass or more of the vinyl aromatic compound and the total amount of the conjugated diene compound used for the polymerization (100% by mass) with respect to the total amount (100% by mass) of the vinyl aromatic compound used for polymerization. ) To the reactor with less than 90% by mass of the conjugated diene compound (hereinafter simply referred to as “Step 1”).
(Step 2) After or simultaneously with Step 1, a polymerization initiator is added to the reactor, and the vinyl aromatic compound and the conjugated diene compound prepared in the reactor are polymerized (hereinafter simply referred to as “Step 2”). ")
(Step 3) After step 2, the step of continuously adding the remainder of the vinyl aromatic compound and the conjugated diene compound to the reactor (hereinafter simply referred to as “step 3”).

  Moreover, the process 2 should just be implemented after the process 1 or simultaneously, and you may implement another process between the process 1 and the process 2. FIG. Furthermore, the process 3 should just be implemented after the process 2, and another process may be implemented between the process 2 and the process 3. FIG.

[Step 1]
The vinyl aromatic compound and the conjugated diene compound in Step 1 of the present embodiment can be respectively polymerized to become a vinyl aromatic compound unit and a conjugated diene compound unit contained in the conjugated diene polymer. In addition, either the vinyl aromatic compound or the conjugated diene compound in step 1 of this embodiment may be added to the reactor first.

<Vinyl aromatic compound>
In Step 1, from the viewpoint of improving randomness, the vinyl aromatic compound added to the reactor is 50% by mass or more and 90% by mass with respect to the total amount (100% by mass) of the vinyl aromatic compound used for the polymerization. % Or more is more preferable, and 100% by mass is particularly preferable.

  The vinyl aromatic compound is not particularly limited as long as it is an aromatic compound having a vinyl group, and examples thereof include vinyl aromatic hydrocarbons. Examples of the vinyl aromatic hydrocarbon include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is preferable.

<Conjugated diene compound>
In Step 1, from the viewpoint of improving randomness, the conjugated diene compound added to the reactor is less than 90% by mass and less than 85% by mass with respect to the total amount (100% by mass) of the conjugated diene compound used for the polymerization. It is more preferable that it is less than 80% by mass.

  Although a conjugated diene compound will not be specifically limited if it is a compound which has a conjugated diene group, For example, a conjugated diene hydrocarbon is mentioned. Examples of the conjugated diene hydrocarbon include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, and 1,3-heptadiene. And 1,3-hexadiene, among which 1,3-butadiene is preferred.

<Ether compounds, amine compounds>
Step 1 is a compound having an ether group or an amino group (hereinafter, each compound is also referred to as “ether compound” or “amine compound”) from the viewpoint of adjusting the 1,2-vinyl bond content and improving randomness. Is preferably added to the reactor.

  The compound having an ether group is not particularly limited. For example, a chain ether compound such as dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; tetrahydrofuran, bis (2-oxolanyl) ethane, 2, 2 -Bis (2-oxolanyl) propane, 1,1-bis (oxolanyl) ethane, 2,2-bis (oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis And cyclic ether compounds such as (3,4,5-trimethyl-2-oxolanyl) propane.

Among the above compounds, from the viewpoint of improving randomness, a cyclic ether represented by the following general formula (A) is preferable, and tetrahydrofuran and 2,2-bis (2-oxolanyl) propane are more preferable.
(In the formula, R _{1 to} R ₄ each independently represents a functional group formed by combining one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, and an oxygen atom. Show.)

Examples of the functional group represented by R ₁ to R _4, is not particularly limited, a hydrogen atom, an alkyl group, and an alkoxy group.

  The compound having an amino group is not particularly limited. For example, as a tertiary amine, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1- Tertiary monoamines such as diethoxytriethylamine and N, N-dimethylformamide isopropyl acetal; N, N, N ′, N′-tetramethylaziminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropanediamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, Tertiary diamine such as N′-tetramethylhexanediamine, dipiperidinopentane, dipiperidinoethane, etc. And the like. Of these tertiary amines, tetraethylenediamine is preferred.

The compound having an amino group may be a compound represented by the following general formula (B).
Wherein R ₁ and R ₂ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. Indicate which one will be.)

The group represented by R ₁ and R ₂ is not particularly limited. For example, methyl, ethyl, propyl, butyl, octyl, cyclopropyl, cyclohexyl, 3-phenyl-1-propyl, isobutyl, decyl, heptyl And phenyl.

  The compound represented by the general formula (B) is not particularly limited. For example, dimethylamine, diethylamine, dibutylamine, dihexylamine, diheptylamine, dihexylamine, dioctylamine, di-2-ethylhexyl. Examples include amines, didecylamine, ethylpropylamine, ethylbutylamine, ethylzylamine, and methylphenethylamine. Moreover, these similar substances that satisfy the condition of the general formula (B) are also included.

In general formula (B), the groups represented by R ₁ and R ₂ may be bonded to form a cyclic structure with the adjacent nitrogen atom, in which case the total number of carbon atoms of R ₁ and R ₂ is , 5 to 12 hydrocarbon groups, which may have an unsaturated bond or a branched structure.

In the case where the groups represented by R ₁ and R ₂ are bonded, examples of the compound represented by the general formula (B) include piperidine, pyrrolidine, hexamethyleneimine, heptamethyleneimine, 2-methylpiperidine, 3- Examples include methylpiperidine, 4-methylpiperidine, and 3,5-dimethylpiperidine. These analogs are also included.

  An amine compound may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the amine compound used is preferably 0.05 mol or more and 3.0 mol or less, more preferably 0.05 mol or more and 2.0 mol or less per 1.0 mol of the organometallic compound which is a polymerization initiator described later. Or less, more preferably 0.05 mol or more and 1.7 mol or less, and still more preferably 0.05 mol or more and 1.5 mol or less. Further, the amine compound may be previously reacted with an organic alkali metal compound that is a polymerization initiator and used as an organic alkali metal amide compound.

<Solvent>
When a solvent is used for the polymerization, the solvent is preferably a hydrocarbon solvent. Examples of the hydrocarbon solvent include hexane, cyclohexane, and benzene. The solvent is preferably added to the reactor in step 1, but may be added in step 2.

[Step 2]
Although it will not specifically limit as a polymerization initiator in the process 2 if a polymerization of a vinyl aromatic compound and a conjugated diene compound can be started, An organic alkali metal compound is preferable. Examples of the organic alkali metal compound include monoorganolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, benzyllithium, piperidinolithium, and pyrrolidinolithium. Compound; polyvalent lithium compound such as dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; organic sodium compound such as sodium naphthalene; organic such as potassium naphthalene A potassium compound is mentioned. Among these, an organolithium compound is preferable.

  A polymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the polymerization initiator used is preferably 0.1 mmol or more and 30 mmol or less, more preferably 0.5 mmol or more and 15 mmol or less, per 1000 g of the vinyl aromatic compound and the conjugated diene compound.

[Step 3]
In step 3, the residues of the vinyl aromatic compound and the conjugated diene compound may be added simultaneously or separately. “Continuous addition” in step 3 means that the flow rate is in the range of 30 to 100,000 g / min and the reactor is not stopped from the start of addition of the remaining vinyl aromatic compound and / or conjugated diene compound to the end of addition. Is to add to. Note that the remainder of the vinyl aromatic compound and conjugated diene compound in Step 3 is the amount of the conjugated diene compound when all of the vinyl aromatic compound used for polymerization in Step 1 is added to the reactor (100% by mass). It means only the remainder.

  The time for continuously adding the residue of the vinyl aromatic compound and the conjugated diene compound is preferably 0.2 minutes or more, more preferably 0.5 minutes or more, from the viewpoint of improving randomness. More preferably, 0 minutes or more. Further, from the viewpoint of suppressing deactivation of the polymerization active terminal, it is preferably less than 120 minutes, more preferably less than 100 minutes, and even more preferably less than 90 minutes.

  When paying attention to the time for adding the vinyl aromatic compound residue, the time for continuously adding the vinyl aromatic compound residue is preferably 0.2 minutes or more from the viewpoint of improving randomness. More preferably, it is 5 minutes or more, and more preferably 1.0 minute or more. Further, from the viewpoint of suppressing the deactivation of the polymerization active terminal, it is preferably less than 30 minutes, more preferably less than 20 minutes, and even more preferably less than 10 minutes.

  When paying attention to the time for adding the residue of the conjugated diene compound, the time for continuously adding the residue of the conjugated diene compound is preferably 0.2 minutes or more from the viewpoint of improving randomness, More preferably, it is more than 1.0 minute, and more preferably is more than 1.0 minute. Further, from the viewpoint of suppressing deactivation of the polymerization active terminal, it is preferably less than 120 minutes, more preferably less than 90 minutes, and even more preferably less than 60 minutes.

  When the time for adding the residue of the vinyl aromatic compound is different from the time for adding the residue of the conjugated diene compound, the completion of the addition of the residue of the vinyl aromatic compound is before completion of the addition of the residue of the conjugated diene compound. Preferably, the time from the completion of the addition of the vinyl aromatic compound residue to the completion of the addition of the conjugated diene compound residue is preferably 1 minute or more, more preferably 5 minutes or more, and more preferably 10 minutes or more. More preferably.

  Viewpoint of improving balance between low hysteresis loss performance and wet grip performance with respect to the total amount of vinyl aromatic compound and total amount of conjugated diene compound (100% by mass) used in polymerization in steps 1 and 3 Therefore, the total amount of the vinyl aromatic compound is preferably 30% by mass or more and 65% by mass or less, and more preferably 30% by mass or more and 60% by mass or less.

  When the vinyl aromatic compound and the conjugated diene compound are polymerized using the above-described polymerization initiator, a conjugated diene polymer having an active terminal can be obtained, and alcohol, water, carbon dioxide gas, etc. are provided at the active terminal as necessary. Can be used to deactivate the active end by a known method.

  The polymerization temperature in Steps 1 to 3 is not particularly limited as long as living anion polymerization proceeds. However, it is preferably 0 to 90 ° C and more preferably 10 to 80 ° C from the viewpoint of productivity. . Moreover, it is preferable that it is 10 to 240 minutes from the viewpoint of productivity, and, as for the polymerization time in process 1-3, it is more preferable that it is 10 to 180 minutes.

[Step 4]
The method for producing a conjugated diene polymer preferably further includes a step of adding a coupling agent to the reactor after step 3 from the viewpoint of the balance between processability and wear resistance. When coupling the conjugated diene polymer obtained in step 3, it is preferable to add a coupling agent to react before deactivating the active terminal.

  When the coupling agent is reacted with the polymerization active terminal of the conjugated diene polymer, the reaction temperature and reaction time are not particularly limited, but are preferably 50 to 80 ° C. and 0.5 minutes or longer.

  The coupling agent may or may not contain a modifying group. The coupling agent is preferably a compound having one or more selected from the group consisting of an alkoxide group, an epoxy group, an ester group, and a halogen group from the viewpoint of reactivity.

  Examples of the coupling agent having an alkoxy group include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, triethoxymethylsilane, triethoxyphenylsilane, Tetramethoxysilane, tetraethoxysilane, 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) propyl] -4-methylpiperazine, 1- [3- (Trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) propyl] -3-ethylimidazolidine, 1- [3- (triethoxysilyl) propyl] -3-methyl Hexahydropyrimidi 1- [3- (dimethoxymethylsilyl) propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilyl) propyl] -1-methyl-1,2,3,4-tetrahydropyrimidine, 3 -[3- (Dimethoxymethylsilyl) propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) propyl] imidazolidine , (2- {3- [3- (trimethoxysilyl) propyl] tetrahydropyrimidin-1-yl} ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1 -[3- (Dimethoxymethylsilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (Tributoxy) L) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (diethoxyethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl] -3- (Trimethylsilyl) imidazolidine, 1- [3- (dimethoxymethylsilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [4- (triethoxysilyl) butyl] -4- (trimethylsilyl) piperazine, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2 -Diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silashic Lopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2 -Silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl)- 1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- ( 3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-dimethoxymethylsilylpropyl) -1 Aza-2-silacyclopentane, and 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentanthris- (trimethoxysilylpropyl) isocyanurate It is done.

  Examples of the compound having an epoxy group include 4,4′-diglycidyl-diphenylmethylamine, 4,4′-diglycidyl-dibenzylmethylamine, diglycidylaniline, diglycidylorthotoluidine, tetraglycidylmetaxylenediamine, and tetraglycidyl. Examples include aminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, and tetraglycidyl-1,3-bisaminomethylcyclohexane.

  Examples of the compound having an ester group include acetic acid methyl ester, acetic acid ethyl ester, adipic acid methyl ester, adipic acid ethyl ester, methacrylic acid methyl ester, and methacrylic acid ethyl ester.

  Examples of the compound having a halogen group include dimethyldichlorosilane, diethyldichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, tetrachlorosilane, dimethyldibromosilane, diethyldibromosilane, methyltribromosilane, ethyltribromosilane, and tetrabromosilane. Can be mentioned.

  Among the coupling agents described above, from the viewpoint of rolling resistance and extrusion processability, tetrachlorosilane, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane is more preferred.

  In the coupling agent described above, the total number of moles of functional groups in the compound is preferably in the range of 0.8 to 3.0 times the number of moles added of the polymerization initiator, 1.0 to 2.5 The range is more preferably doubled, and more preferably 1.0 to 2.0 times. The conjugated diene polymer to be obtained is preferably 0.8 times or more in order to obtain a sufficient modification rate, and a branched polymer component is obtained by coupling polymer ends to improve extrusion processability. Is preferably 3.0 times or less from the viewpoint of the coupling agent cost.

[Conjugated diene polymer]
The conjugated diene polymer of this embodiment preferably has a coupling rate of 5.0% to 90%, more preferably 10% to 85%. When the coupling rate is within the above range, a vulcanizate that has a better balance between the low hysteresis loss performance and the wet skid resistance performance and that satisfies the wear resistance tends to be obtained.

  As a measuring method of a coupling rate, it can obtain | require from the area ratio at the time of measuring using a polystyrene-type gel column by gel permeation chromatography (GPC). Specifically, it can measure by the method as described in the Example mentioned later.

  The conjugated diene polymer of the present embodiment may be modified. As described later, when silica is added as a reinforcing filler and a vulcanized product is used, low hysteresis loss performance and wet skid resistance are achieved. In order to achieve an excellent balance with performance, the modification rate, that is, the content of the polymer containing a modifying group resulting from a polymerization initiator or a coupling agent may be 15% by mass or more.

  The denaturation rate can be measured by chromatography capable of separating the denaturing component and the non-denaturing component. As a measurement method, a silica column capable of adsorbing a denatured component by gel permeation chromatography (GPC) and a polystyrene gel column not adsorbing a denatured component are added to a sample using standard polystyrene not adsorbed on the column as an internal standard. By measuring, the denaturation rate can be obtained from the obtained RI difference. Specifically, it can measure by the method as described in the Example mentioned later.

  The amount of the bound vinyl aromatic compound in the conjugated diene polymer of the present embodiment obtained by Step 1 to Step 4 is 30% by mass or more from the viewpoint of improving the balance of low hysteresis loss performance, wet grip performance, and wear resistance. It is preferably 65% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. When the amount of the bound vinyl aromatic compound is within the above range, a vulcanizate having a further excellent balance between low hysteresis loss performance and wet skid resistance performance and satisfactory wear resistance tends to be obtained.

  The amount of the bound vinyl aromatic compound can be measured by ultraviolet absorption of the phenyl group, and the amount of bound conjugated diene can also be obtained from this. Specifically, it can be measured by the method according to the examples described later, that is, according to the method for measuring the amount of bound styrene.

  The vinyl aromatic compound in the conjugated diene polymer may be uniform or non-uniformly distributed in the copolymer chain. When used in a tire, the composition distribution of the conjugated diene compound unit and the vinyl aromatic compound unit in the polymer is preferably uniform in the molecular chain. As an index for judging whether or not the molecular chain is uniform, there is a content of a block vinyl aromatic compound, and an isolated vinyl aromatic compound, that is, a vinyl aromatic compound having one chain of vinyl aromatic compound units. 40% by mass or more of the total bonded vinyl aromatic compound, a long-chain block vinyl aromatic compound, that is, a vinyl aromatic compound having a chain of 8 or more vinyl aromatic compound units (block vinyl aromatic compound) is a fully bonded vinyl aromatic compound It is preferable that they are 0.5 mass% or more and less than 3.5 mass%. When the content of the block vinyl aromatic compound is within the above range, a vulcanizate having a further excellent balance between low hysteresis loss performance and wet skid resistance performance and satisfactory wear resistance tends to be obtained. In the copolymer with styrene which is a vinyl aromatic compound, isolated styrene, that is, styrene having a chain of one styrene unit is 40% by mass or more of all bonded styrene, long-chain block styrene, that is, styrene unit. It is preferable that styrene (block styrene) having a chain of 8 or more is 0.5% by mass or more and 3.5% by mass or less of the total bonded styrene.

  For example, the content of block styrene as the content of vinyl aromatic compound can be measured by the method described in the examples described later.

  The polymerization conversion rate of the vinyl aromatic compound used for the polymerization is preferably 93% or more, and more preferably 95% or more, from the viewpoints of productivity and improvement in the randomness of the polymer. When the polymerization conversion rate is lower than the above range, there is a high possibility that a vinyl aromatic compound block is generated at the end of the polymer.

  The polymerization conversion rate can be calculated from the vinyl aromatic compound addition amount and the vinyl aromatic compound block content used for the polymerization, and specifically can be calculated by the method described in the examples described later.

  It is preferable that the polymerization conversion rate of the vinyl aromatic compound at the end of the reaction is high and the randomness in the conjugated diene polymer is high. That is, it is preferable that the polymerization conversion rate of the vinyl aromatic compound is 93% or more and the content of the block vinyl aromatic compound is 5.0% by mass or less.

  The 1,2-vinyl bond content in the polymerized conjugated diene bond unit polymerized by Step 1 to Step 4 is not particularly limited, but is preferably 10 mol% to 40 mol%, preferably 12 mol%. More preferably, it is 35 mol% or less. When the 1,2-vinyl bond content is within the above range, a vulcanizate that has a further excellent balance between low hysteresis loss performance and wet skid resistance performance and that satisfies wear resistance tends to be obtained.

  When the conjugated diene polymer is a copolymer of butadiene and styrene, the vinyl bond is contained in the butadiene bond unit by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The amount (1,2-bond amount) can be determined. Specifically, it can measure by the method as described in the Example mentioned later.

  The conjugated diene polymer is not particularly limited as the composition distribution of each monomer in the random copolymer chain, for example, a completely random copolymer close to a statistical random composition, and the composition is tapered. Examples include a distributed tapered (purchased) random copolymer. The bonding mode of the conjugated diene, that is, the composition such as 1,4-bond or 1,2-bond may be uniform or distributed.

  The amount of cis 1,4 bond in the conjugated diene bond unit is not particularly limited, and is preferably 8.0 mol 5 or more and 99 mol% or less, more preferably 20 mol% or more and 98 mol% or less, and further preferably Is 25 mol% or more and 90 mol% or less. By setting the amount of cis 1,4 bond within the above range, the rolling resistance characteristics tend to be better.

  The bound vinyl aromatic compound amount of the conjugated diene polymer of this embodiment and the vinyl bond content in the conjugated diene bond unit are in the above range, and the glass transition temperature of the conjugated diene polymer is −45 ° C. or more and −10 When the temperature is in the range of 0 ° C. or lower, when a vulcanized product is used, the balance between low hysteresis loss performance, wet skid resistance performance, and wear resistance performance tends to be more excellent.

  The molecular weight of the conjugated diene polymer of the present embodiment is preferably 50000 or more and 200000 or less, more preferably 70000 or more and 1800000 or less, from the viewpoint of processability and the like (weight average molecular weight: polystyrene conversion).

  The molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably 1.0 or more and 3.0 or less, more preferably 1.1 or more and 2.2 or less from the viewpoint of processability and the like. A weight average molecular weight and a number average molecular weight can be measured by the method as described in the Example mentioned later.

  The conjugated diene polymer of this embodiment preferably contains a rubber stabilizer from the viewpoint of suppressing gel formation after polymerization and improving the stability during processing.

  The rubber stabilizer is not particularly limited and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4′- Antioxidants such as hydroxy-3 ′, 5′-di tert-butylphenol) propionate and 2-methyl-4,6-bis [(octylthio) methyl] phenol are preferred.

  In addition, the conjugated diene polymer of the present embodiment can further contain an extending oil as necessary in order to further improve the processability.

  The method for adding the extender oil to the conjugated diene copolymer is not particularly limited, but a method in which the extender oil is added to the polymer solution and mixed to obtain an extender polymer solution is preferably removed.

  The extension oil is not particularly limited, and examples thereof include aroma oil, naphthenic oil, and paraffin oil. Among these, from the viewpoint of environmental safety and prevention of oil bleed, an aromatic substitute oil having a polycyclic aromatic (PCA) component of 3.0% by mass or less by the IP346 method is preferable.

  Examples of the aroma substitute oil include TDAE (Treated Distillate Aromatic Extracts) shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), MES (Mil Extraction Solvate), eXt.

  The content of the extending oil is not particularly limited, but is preferably 10 parts by mass or more and 60 parts by mass or less, and more preferably 20 parts by mass or more and 37.5 parts by mass with respect to the total amount (100 parts by mass) of the conjugated diene polymer. It is below mass parts.

  As a method for obtaining the conjugated diene polymer of the present embodiment from a solvent, a known desolvation method can be used. For example, after separating the solvent by steam stripping or the like, the conjugated diene polymer is separated by filtration, and further dehydrated and dried to obtain a conjugated diene polymer, concentrated in a flushing tank, and further vented extruder The method of devolatilizing with a etc. and the method of devolatilizing directly with a drum dryer etc. are mentioned.

[Method for Producing Modified Conjugated Diene Polymer Composition]
The method for producing the modified conjugated diene polymer composition of the present embodiment includes a rubber component containing the conjugated diene polymer described above, and 0.5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the rubber component. And a silica-based inorganic filler. The rubber component contains 20% by mass of the conjugated diene polymer with respect to the total amount (100% by mass) of the rubber component.

Silica-based inorganic filler refers to solid particles having the chemical formula SiO ₂ or Si ₃ Al as a main component, for example, silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite. And inorganic fibrous materials such as glass fibers.

  Further, a silica-based inorganic filler having a hydrophobic surface, or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. In particular, silica and glass fiber are preferable.

  As silica, dry process white carbon, wet process white carbon, synthetic silicate white carbon, what is called colloidal silica, or the like can be used. These particles preferably have a particle size of 0.01 μm or more and 150 μm or less.

  Further, in the conjugated diene polymer composition of the present embodiment, the average dispersed particle size is 0.05 μm or more and 1.0 μm or less in order to sufficiently exhibit the addition effect of silica by dispersing silica. The thickness is preferably 0.05 μm or more and 0.5 μm or less.

  The compounding amount of the silica-based inorganic filler in the conjugated diene polymer composition of the present embodiment is 0.5 parts by mass or more and 300 parts by mass or less, preferably 5.0 parts by mass with respect to 100 parts by mass of the rubber component. Part to 200 parts by mass, more preferably 20 parts to 100 parts by mass.

  When the compounding amount of the silica-based inorganic filler is 0.5 parts by mass or more, the function as a reinforcing filler can be effectively exhibited, and when the compounding amount is 300 parts by mass or less, a conjugated diene polymer. Inside, the dispersibility of the filler becomes good, and excellent processability and high mechanical strength are obtained.

  In this embodiment, the method for mixing the rubber component and the silica-based inorganic filler is not particularly limited, and a known method can be used. For example, a melt kneading method using a general blender such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc., after dissolving and mixing each component, and a solvent The method of removing by heating is mentioned. Among these, the melt kneading method using a roll, a Banbury mixer, a kneader, and an extruder is preferable from the viewpoints of productivity and good kneading properties.

  Further, the rubber component and the silica-based inorganic filler may be kneaded in their entirety at the same time, or each may be kneaded in a plurality of times.

  The method for producing a conjugated diene polymer composition of the present embodiment may be vulcanized using a vulcanizing agent. As the vulcanizing agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds can be used. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like.

  Although the usage-amount of a vulcanizing agent is not specifically limited, It is preferable that it is 0.01 to 20 mass parts with respect to 100 mass parts of rubber components, More preferably, it is 0.1 to 15 mass parts It is as follows.

  In vulcanization, a vulcanization accelerator may be further used. Examples of the vulcanization accelerator include sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, and dithiocarbamate.

  Further, a vulcanization aid may be further used. Examples of the vulcanization aid include zinc white and stearic acid.

  The amount of these vulcanization accelerators or vulcanization aids used is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component. 15 parts by mass or less.

  In the method for producing a conjugated diene polymer composition of this embodiment, a rubber softener may be further blended in order to improve processability. Preferred examples of the rubber softener include mineral oil and liquid or low molecular weight synthetic softeners.

  A mineral oil rubber softener called process oil or extender oil, which is generally used for the purpose of softening, increasing the volume and improving processability of rubber, is a mixture of aromatic rings, naphthene rings, and paraffin chains. Those with 50% or more of the total carbon number are called paraffinic, those with 30-45% naphthenic ring carbon number are naphthenic, and those with 30% aromatic carbon number are aromatic. be called.

  The rubber softener used in the conjugated diene polymer composition of the present embodiment is preferably a naphthenic and / or paraffinic one.

  As the synthetic softener, for example, polybutene, low molecular weight polybutadiene, or the like can be used, but the mineral oil rubber softener gives better results.

  In the method for producing a conjugated diene polymer composition of the present embodiment, when a rubber softener is blended, the blending amount of the rubber softener is 0 part by mass or more and 100 parts by mass with respect to 100 parts by mass of the rubber component. It is preferably no greater than 10 parts, more preferably no less than 10 parts by mass and no greater than 90 parts by mass, and even more preferably no less than 30 parts by mass and no greater than 90 parts by mass.

  When the blending amount of the rubber amount softening agent is within the above range, processability is good, bleeding out can be suppressed, and stickiness on the surface tends to be suppressed.

  The rubber component of the present embodiment can contain a rubbery polymer different from the conjugated diene polymer described above in combination with the conjugated diene polymer described above.

  As such a rubbery polymer, for example, a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound or a hydrogenated product thereof, a non-diene polymer, And natural rubber.

  Specifically, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene block copolymerized Examples thereof include styrene-based elastomers such as coalesced or hydrogenated products thereof, and acrylonitrile-butadiene rubber or hydrogenated products thereof.

  Non-diene polymers include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, olefin-based elastomers such as ethylene-octene rubber, butyl rubber, brominated butyl rubber, and acrylic rubber. , Fluoro rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, and polysulfide rubber.

  These rubber-like polymers may be modified rubbers provided with functional groups. These may be used alone or in combination.

  When the rubber component is obtained by combining the above-mentioned various rubber-like polymers with the conjugated diene polymer, the rubber-like polymer is 1.0 part by mass or more and 400 parts by mass with respect to 100 parts by mass of the conjugated diene polymer. It is preferable that it is below, More preferably, it is 5.0 to 200 mass parts, More preferably, it is 10 to 100 mass parts.

  Various additives can be blended with the conjugated diene polymer composition of the present embodiment, if necessary, within a range not impairing the effects of the invention.

  Examples of additives include softeners, heat stabilizers, antistatic agents, weathering stabilizers, anti-aging agents, fillers, colorants, and lubricants.

  Examples of the softening agent that can be blended as necessary to adjust the hardness and fluidity of the product include liquid paraffin, castor oil, and linseed oil.

  Examples of the filler include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.

  Known materials can be applied as the heat resistance stabilizer, antistatic agent, weather resistance stabilizer, anti-aging agent, colorant, and lubricant.

[Method for producing rubber composition]
The manufacturing method of the rubber composition of this embodiment has the process of carrying out the bridge | crosslinking process of the conjugated diene type polymer composition obtained by said manufacturing method. The conjugated diene polymer composition described above can be subjected to a crosslinking treatment by means such as heat treatment.

[Tire manufacturing method]
The tire manufacturing method of the present embodiment includes a step of molding a tire including the rubber composition obtained by the above manufacturing method. In addition to tires, the rubber composition described above can be molded into anti-vibration rubber and various industrial products.

  Hereinafter, although a specific Example and a comparative example are given and this embodiment is described in detail, this embodiment is not limited to the following examples.

(Physical property 1) Amount of bound styrene, polymerization conversion of styrene A sample of a conjugated diene polymer was used as a chloroform solution, and the amount of bound styrene (% by mass) was measured by UV 254 nm absorption by the phenyl group of styrene. As a measuring device, “V-550” manufactured by JASCO Corporation was used. The polymerization conversion rate (%) of styrene was calculated by the following formula.
Polymerization conversion rate of styrene (%) = [(bound styrene amount (mass%)) / (styrene amount used for polymerization (mass%))] × 100

(Physical property 2) Microstructure of butadiene part (1,2-vinyl bond content)
A sample of a conjugated diene polymer is made into a thin film, and an infrared spectrum is 600 to 1000 cm by a single reflection ATR method (attenuated total reflection) using FT-IR “Spectrum 100” manufactured by PerkinElmer Japan. ^-1 was measured, and the absorbance at a predetermined wave number was used to obtain the microstructure (%) of the butadiene portion according to the formula of the Hampton method.

(Physical Property 3) Block Styrene Content According to the method of Kolthoff, an osmium acid decomposition product of a conjugated diene polymer sample was obtained for measurement. Using this decomposition product, insoluble polystyrene corresponding to block polystyrene was precipitated in methanol. The amount of insoluble polystyrene was quantified, and the block styrene content (% by mass) per polymer was calculated. In addition, the content (mass%) in all styrene of one styrene unit chain having one styrene unit and the content (mass%) in all styrene of a styrene long chain in which 8 or more styrene units are connected are represented by Tanaka et al. According to the method (Polymer, 22, 1721 (1981)), the styrene-butadiene copolymer rubber was decomposed with ozone and then analyzed by gel permeation chromatography (GPC).

(Evaluation 1) Randomness Randomness was evaluated according to the following evaluation criteria.
○: The polymerization conversion of styrene determined in (Physical Property 1) is 93% or more, and the block styrene content determined in (Physical Property 3) is 3.5% by mass or less.
X: The polymerization conversion of styrene determined in (Physical Property 1) is less than 93%, or the block styrene content determined in (Physical Property 3) exceeds 3.5% by mass.

(Physical property 4) Weight permeation chromatography using weight average molecular weight, number average molecular weight, molecular weight distribution, coupling rate, using a conjugated diene polymer as a sample and connecting the following three columns using polystyrene gel as a filler. The chromatogram is measured using a graph (GPC), the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by a calibration curve using standard polystyrene, the molecular weight distribution (Mw / Mn) is calculated, and the molecular weight A distribution curve was created. From the prepared molecular weight distribution curve, the total peak area was taken as 100, and the area obtained by subtracting the peak area of the base polymer from the total peak area was taken as the coupling rate (%). Other measurement conditions were as follows.
Eluent: Tetrahydrofuran (THF)
Guard column: “TSK guard column HHR-H” manufactured by Tosoh Corporation
Column: “TSKgel G6000HHR” manufactured by Tosoh Corporation
"TSKgel G5000HHR",
"TSKgel G4000HHR"
Oven temperature: 40 ° C
THF flow rate: 1.0 mL / min RI detector: “HLC8020” manufactured by Tosoh Corporation
Sample: 200 μL of a solution of 10 mg of conjugated diene polymer dissolved in 20 mL of tetrahydrofuran (THF)

(Physical property 5) Modification rate GPC column with silica gel as a filler makes use of the property that the modified component is adsorbed. Sample of conjugated diene polymer and standard polystyrene with molecular weight of 5000 (polystyrene does not adsorb on the column) Using a polystyrene-based gel column GPC similar to (Physical property 4) and a silica-based column (guard column: DIOL 4.6 × 12.5 mm 5 micron, column: Zorbax PSM-1000S, PSM-300S, PPC-60S, oven temperature 40 ° C., THF flow rate 0.5 mL / min) GPC (manufactured by Tosoh Corporation “CCP8020 series build-up type GPC system: AS-8020, SD-8022, CCPS, CO-8020, RI-8021”) ) And both chromatograms were measured using an RI detector. The amount of modification on the silica column was measured from these differences to determine the modification rate (%). As a sample, 10 mg was dissolved in 20 mL of THF together with 5 mg of standard polystyrene, and 200 μL was injected for measurement.

As a more specific procedure, the peak area of the chromatogram using the polystyrene column is defined as 100, the peak area of the sample polystyrene area is P1, the peak area of the standard polystyrene is P2, and the peak of the chromatogram using the silica column is used. The total area was set to 100, the sample peak area was P3, the peak area of standard polystyrene was P4, and the modification rate (%) was calculated using the following formula.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100

[Example 1]
An autoclave having an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane from which impurities had been previously removed, 294 g of styrene, 203 g of 1,3 butadiene, tetrahydrofuran (in the table, “THF”) 3.16 g was charged to the reactor under a nitrogen atmosphere and the mixture was heated to 65.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium (abbreviated as “n-BuLi” in the table) was supplied to the reactor so that the amount of lithium added was 1.65 mmol. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 76.0 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane (referred to as “Cup-1” in the table) was added to the reactor, and a coupling reaction was carried out for 5 minutes at a temperature of 74.0 ° C. . The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample A) having a modifying component was obtained.

  As a result of analyzing Sample A, the bound styrene content was 41.2% by mass, and the 1,2-vinyl bond content was 20.1% by mass. Details of the polymerization conditions of Sample A are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

[Example 2]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 304 g of 1,3 butadiene, and 3.16 g of tetrahydrofuran were previously removed from the nitrogen atmosphere. The reactor was charged under and the mixture was heated to 63.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. After 14 minutes from the start of the reaction, 102 g of 1,3 butadiene was continuously added over 1 minute. The final peak temperature in the reactor reached 78.0 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed for 5 minutes at a temperature of 78.0 ° C. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample B) having a modifying component was obtained.

  As a result of analyzing Sample B, the bound styrene content was 40.1% by mass, and the 1,2-vinyl bond content was 20.9% by mass. Details of the polymerization conditions of Sample B are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 3
An autoclave having an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 142 g of 1,3 butadiene, and 3.16 g of tetrahydrofuran were previously removed from the nitrogen atmosphere. The reactor was charged under and the mixture was heated to 66.1 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. Nine minutes after the start of the reaction, 264 g of 1,3 butadiene was continuously added over 2.5 minutes. The final peak temperature in the reactor reached 73.0 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was carried out at a temperature of 73.0 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (Sample C) having a modifying component was obtained.

  As a result of analyzing Sample C, the amount of bonded styrene was 41.6% by mass, and the content of 1,2-vinyl bond was 19.7% by mass. Details of the polymerization conditions of Sample C are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 4
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 234 g of styrene, 203 g of 1,3 butadiene, and 3.16 g of tetrahydrofuran, from which impurities had been removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 66.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. Ten minutes after the start of the reaction, 60 g of styrene was continuously added over 0.4 minutes, and then 203 g of 1,3 butadiene was continuously added over 2.5 minutes. The final peak temperature in the reactor reached 73.4 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature of 73.4 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (sample D) having a modifying component was obtained.

  As a result of analyzing Sample D, the bound styrene content was 40.2% by mass, and the 1,2-vinyl bond content was 20.7% by mass. Details of the polymerization conditions of Sample D are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 5
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene, and 6.32 g of tetrahydrofuran were previously removed from the nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 76.6 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature of 76.6 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample E) having a modifying component was obtained.

  As a result of analyzing Sample E, the amount of bound styrene was 41.2% by mass, and the content of 1,2-vinyl bond was 21.2% by mass. Details of the polymerization conditions of Sample E are shown in Table 1, and physical properties and results of evaluation are shown in Table 3.

Example 6
An autoclave having an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene, and 1.26 g of tetrahydrofuran were previously removed from the nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 72.0 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature condition of 72.0 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample F) having a modifying component was obtained.

  As a result of analyzing Sample F, the bound styrene content was 39.9% by mass, and the 1,2-vinyl bond content was 17.8% by mass. Details of the polymerization conditions of Sample F are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 7
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.6 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.27 mmol. 16 minutes after the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 74.2 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was carried out at a temperature of 74.2 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample G) having a modifying component was obtained.

  As a result of analyzing Sample G, the amount of bound styrene was 40.2% by mass, and the content of 1,2-vinyl bond was 19.9% by mass. Details of the polymerization conditions of Sample G are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 8
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.0 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 2.42 mmol. Ten minutes after the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 76.9 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature of 76.9 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample H) having a modifying component was obtained.

  As a result of analyzing Sample H, the amount of bonded styrene was 40.1% by mass, and the content of 1,2-vinyl bond was 19.6% by mass. Details of the polymerization conditions of Sample H are shown in Table 1, and physical properties and results of evaluation are shown in Table 3.

Example 9
An autoclave having an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 378 g of styrene, 161 g of 1,3 butadiene, and 3.16 g of tetrahydrofuran were previously removed from the nitrogen atmosphere. The reactor was charged under and the mixture was heated to 63.8 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. 15 minutes after the start of the reaction, 161 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 76.1 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature condition of 76.1 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (Sample I) having a modifying component was obtained.

  As a result of analyzing Sample I, the amount of bonded styrene was 51.3% by mass, and the content of 1,2-vinyl bond was 20.1% by mass. Details of the polymerization conditions of Sample I are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 10
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 224 g of styrene, 238 g of 1,3 butadiene, and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, The reactor was charged under and the mixture was heated to 64.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. 15 minutes after the start of the reaction, 238 g of 1,3 butadiene was continuously added over 2.5 minutes. The final peak temperature in the reactor reached 76.2 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature of 76.2 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (Sample J) having a modifying component was obtained.

  As a result of analyzing Sample J, the bound styrene content was 31.7% by mass, and the 1,2-vinyl bond content was 19.7% by mass. Details of the polymerization conditions of Sample J are shown in Table 1, and physical properties and evaluation results are shown in Table 3.

Example 11
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was added to a mixture of 1.65 mmol of piperidine, 3.30 mmol of tetrahydrofuran and cyclohexane at room temperature so that the amount of lithium added was 1.65 mmol, and piperidinolithium (in the table, “ Abbreviated as “Pip-Li”) and the entire amount was fed to the reactor. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 75.3 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature condition of 75.3 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample K) having a modifying component was obtained.

  As a result of analyzing sample K, the amount of bound styrene was 40.5% by mass, and the content of 1,2-vinyl bond was 19.4% by mass. Details of the polymerization conditions of Sample K are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

Example 12
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was added to a mixture of 1.65 mmol of pyrrolidine, 3.30 mmol of tetrahydrofuran and cyclohexane at room temperature so that the addition amount of lithium was 1.65 mmol, and pyrrolidinolithium (in the table, “Pyr” Abbreviated as “-Li”), and the whole amount was fed to the reactor. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 75.0 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature condition of 75.0 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (sample L) having a modifying component was obtained.

  As a result of analyzing the sample L, the amount of bound styrene was 40.7% by mass, and the content of 1,2-vinyl bond was 19.7% by mass. Details of the polymerization conditions of Sample L are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

Example 13
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene, 2,2-bis (2- Oxolanyl) propane (abbreviated as “BOP” in the table) was charged to the reactor under a nitrogen atmosphere and the mixture was heated to 65.0 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. Eleven minutes after the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 74.0 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed for 5 minutes at a temperature of 74.0 ° C. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (Sample M) having a modifying component was obtained.

  As a result of analyzing sample M, the amount of bound styrene was 40.4% by mass, and the content of 1,2-vinyl bond was 24.8% by mass. Details of the polymerization conditions of Sample M are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

Example 14
An autoclave having an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane from which impurities had been previously removed, 294 g of styrene, 203 g of 1,3 butadiene, tetramethylethylenediamine (in the table, “ Abbreviated as “TMEDA”.) 0.02 g was charged to the reactor under a nitrogen atmosphere and the mixture was heated to 65.0 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. 17 minutes after the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 72.2 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed at a temperature condition of 72.2 ° C. for 5 minutes. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (Sample N) having a modifying component was obtained.

  As a result of analyzing Sample N, the bound styrene content was 39.8% by mass, and the 1,2-vinyl bond content was 23.6% by mass. Details of the polymerization conditions of Sample N are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

Example 15
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 76.7 ° C. After 1 minute from the peak temperature, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane (referred to as “Cup-2” in the table) was added to the reactor. 0.0825 mmol was added and a coupling reaction was carried out for 5 minutes at a temperature of 76.7 ° C. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (sample O) having a modifying component was obtained.

  As a result of analyzing Sample O, the amount of bound styrene was 40.9% by mass, and the content of 1,2-vinyl bond was 20.0% by mass. Details of the polymerization conditions of Sample O are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

Example 16
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been previously removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 65.5 ° C. with stirring. Next, to the mixture of 1.65 mmol of piperidine, 3.30 mmol of tetrahydrofuran and cyclohexane, a cyclohexane solution of n-butyllithium was added at room temperature so as to be 1.65 mmol as a lithium addition amount to prepare piperidinolithium. Was fed to the reactor. After 13 minutes from the start of the reaction, 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 75.7 ° C. After 1 minute from the peak temperature, 0.0825 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was 75.7 ° C. The coupling reaction was carried out for 5 minutes under the conditions. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (sample P) having a modifying component was obtained.

  As a result of analyzing Sample P, the amount of bound styrene was 41.0% by mass, and the content of 1,2-vinyl bond was 19.8% by mass. Details of the polymerization conditions of Sample P are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

[Comparative Example 1]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 294 g of styrene, 406 g of 1,3 butadiene, and 3.16 g of tetrahydrofuran were previously removed from the nitrogen atmosphere. The reactor was charged under and the mixture was heated to 57.4 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. The final peak temperature in the reactor reached 79.1 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was carried out for 5 minutes at a temperature of 79.1 ° C. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample Q) having a modifying component was obtained.

  As a result of analyzing Sample Q, the amount of bound styrene was 36.3% by mass, and the content of 1,2-vinyl bond was 19.8% by mass. Details of the polymerization conditions of Sample Q are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

[Comparative Example 2]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 88 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 67.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. Eleven minutes after the start of the reaction, 206 g of styrene was continuously added over 1 minute, and 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 75.7 ° C. One minute after the peak temperature, 0.0825 mmol of tetrachlorosilane was added to the reactor, and a coupling reaction was performed for 5 minutes at a temperature condition of 75.7 ° C. The reaction was terminated by adding 1.45 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (sample R) having a modifying component was obtained.

  As a result of analyzing Sample R, the bound styrene content was 33.2% by mass, and the 1,2-vinyl bond content was 20.2% by mass. Details of the polymerization conditions of Sample R are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

[Comparative Example 3]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 5417 g of cyclohexane, 88 g of styrene, 203 g of 1,3 butadiene and 3.16 g of tetrahydrofuran, from which impurities had been removed, were added in a nitrogen atmosphere. The reactor was charged under and the mixture was heated to 67.5 ° C. with stirring. Next, a cyclohexane solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 1.65 mmol. Eleven minutes after the start of the reaction, 206 g of styrene was continuously added over 1 minute, and 203 g of 1,3 butadiene was continuously added over 2 minutes. The final peak temperature in the reactor reached 76.0 ° C. After 1 minute from the peak temperature, the mixture was stirred for 30 minutes at a temperature condition of 76.0 ° C. The reaction was terminated by adding 1.65 mmol of methanol to the polymer solution. After adding 1.5 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying process is performed by a dryer. A styrene-butadiene copolymer (sample R) having a modifying component was obtained.

  As a result of analyzing Sample R, the amount of bound styrene was 41.4% by mass, and the content of 1,2-vinyl bond was 19.9% by mass. Details of the polymerization conditions of Sample S are shown in Table 2, and physical properties and evaluation results are shown in Table 4.

  Even when the conjugated diene polymer according to the present invention is a conjugated diene polymer composition combined with an inorganic filler, each of wet skid characteristics, low hysteresis loss, wear resistance, fracture strength, steering stability, etc. Excellent balance of physical properties and workability, so it has industrial applicability in fields such as automobile interior / exterior products, anti-vibration rubber, belts, footwear, foams, various industrial parts, tire applications, etc. is there.

Claims (14)

A method for producing a conjugated diene polymer comprising a vinyl aromatic compound unit and a conjugated diene compound unit,
Having the following steps 1 to 3,
A method for producing a conjugated diene polymer.
(Step 1) The total amount of the vinyl aromatic compound used in the polymerization is 50% by mass or more, and the total amount of the conjugated diene compound used in the polymerization is less than 90% by mass. Step of adding the conjugated diene compound to the reactor (Step 2) After or simultaneously with Step 1, a polymerization initiator is added to the reactor, and the vinyl aromatic compound and the conjugated diene prepared in the reactor are added. Step of polymerizing a system compound (Step 3) Step of continuously adding the residue of the vinyl aromatic compound and the conjugated diene compound to the reactor after Step 2 The step 1 is a step of preparing 100% by mass of the vinyl aromatic compound in the reactor with respect to the total amount of the vinyl aromatic compound used for polymerization.
The method for producing a conjugated diene polymer according to claim 1. In the step 3, the time for continuously adding the vinyl aromatic compound and the residue of the conjugated diene compound is 0.2 minutes or more and less than 120 minutes,
The manufacturing method of the conjugated diene polymer of Claim 1 or 2. Step 1 is a step of further adding a compound having an ether group or an amino group to the reactor.
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-3. The compound is a compound having an ether group, and is a compound represented by the following general formula (A).
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-4.
(In the formula, R _{1 to} R ₄ each independently represents a functional group formed by combining one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, and an oxygen atom. Show.) After the step 3, further comprising adding a coupling agent to the reactor;
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-5. The coupling agent is a compound having one or more selected from the group consisting of an alkoxide group, an epoxy group, an ester group, and a halogen group.
The manufacturing method of the conjugated diene polymer of Claim 6. The total amount of the vinyl aromatic compound is 30% by mass or more and 65% by mass or less with respect to the total amount of the vinyl aromatic compound and the total amount of the conjugated diene compound used for polymerization.
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-7. The polymerization conversion rate of the vinyl aromatic compound is 93% or more.
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-8. The content of the block vinyl aromatic compound in the conjugated diene polymer is 0.5% by mass or more and less than 3.5% by mass.
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-9. The 1,2-vinyl bond content in the conjugated diene polymer is 10% by mass or more and 40% by mass or less.
The manufacturing method of the conjugated diene polymer as described in any one of Claims 1-10. A rubber component containing the conjugated diene polymer obtained by the production method according to any one of claims 1 to 11, and 0.5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the rubber component. A step of mixing a silica-based inorganic filler,
The rubber component contains the conjugated diene polymer in an amount of 20% by mass or more based on the total amount of the rubber component.
A method for producing a conjugated diene polymer composition. The method further comprises a step of crosslinking the conjugated diene polymer composition obtained by the production method according to claim 12.
A method for producing a rubber composition. It has the process of shape | molding the tire containing the rubber composition obtained by the manufacturing method of Claim 13.
Tire manufacturing method.