JP2020180174A - Method for producing conjugated diene polymer, method for producing conjugated diene polymer composition, method for producing tire, and vinylation agent - Google Patents

Abstract

To provide a method for efficiently producing a conjugated diene polymer having a high coupling reaction rate.SOLUTION: The present invention provides a method for producing a conjugated diene polymer, in which, in the presence of a polar compound represented by formula (1), a polymerization initiator is used to polymerize a conjugated diene polymer (R1-R3 each denote a C1-20 hydrocarbon group that may have a substituent or may have O, N, P, S, or the like. R4 denotes a C1-20 hydrocarbon group that may have a substituent or may have a hetero atom of O, N, P, S, or H, or the like).SELECTED DRAWING: None

Description

The present invention relates to a method for producing a conjugated diene-based polymer, a method for producing a conjugated diene-based polymer composition, a method for producing a tire, and a vinylizing agent.

Conventionally, SSBR polymerization (polymerization of styrene-butadiene rubber by solution polymerization) using a polar compound having an ether group or an amino group as a vinylizing agent has been performed.
For example, when tetrahydrofuran (THF) or 2,2-bis (2-oxolanyl) propane is used as a vinylizing agent to produce SSBR having a low 1,2-vinyl bond content by batch polymerization, a high monomer is used. In order to maintain the conversion rate (particularly, the high monomer conversion rate of styrene monomer, which is less reactive than butadiene monomer) and high randomness, it is necessary to polymerize under high temperature conditions to some extent. On the other hand, when the polymerization temperature becomes high, the living end of the polymer is heat-deactivated, so that the reaction rate with the coupling agent decreases.
In addition, a method using an alkaline earth metal-based initiator as the polymerization initiator has also been proposed, but it is known that the reaction rate with the coupling agent is extremely lowered even when the polymerization is carried out by this method. There is.

Conventionally, a technique has been proposed in which a conjugated diene compound is added to a reactor in multiple stages in the presence of THF to obtain a copolymer having a high monomer conversion rate and good randomness in a polymerization temperature range of 0 to 90 ° C. (See, for example, Patent Document 1).
Further, a technique for producing SSBR containing a low vinyl bond using an alkaline earth metal as a polymerization initiator in the presence of THF has been proposed (see, for example, Patent Document 2).

JP-A-2017-210543 Japanese Unexamined Patent Publication No. 1-230647

However, in the technique described in Patent Document 1, since it is necessary to add a monomer in the middle of the polymerization step, the polymerization system is constantly monitored in order to stably obtain a polymer having a desired structure. , It is necessary to control the polymerization reaction appropriately, and there is a problem that the operation is complicated. In addition, there is a problem that the reaction time until a sufficient monomer conversion rate can be obtained tends to be longer than that of polymerization by adding a monomer to a reactor in a general one step.
In the technique described in Patent Document 2, it is possible to set conditions for obtaining a copolymer having a high monomer conversion rate, few styrene chains, and good randomness, but in this case, the reaction rate with the coupling agent. Has a problem of becoming extremely low.

Therefore, in the present invention, a method for producing a conjugated diene polymer capable of stably producing a conjugated diene polymer having a high coupling reaction rate with a high monomer conversion rate in a short reaction time is provided. The purpose is to provide.

As a result of diligent research and study in order to solve the above-mentioned problems of the prior art, the present inventors polymerize a conjugated diene polymer using a polymerization initiator in the presence of a polar compound having a predetermined structure. By doing so, it was found that the problems of the prior art can be solved, and the present invention has been completed.
That is, the present invention is as follows.

[1]
A conjugated diene polymer having a step of polymerizing a conjugated diene polymer using a polymerization initiator in the presence of a polar compound represented by the following general formula (1) and / or general formula (2). Production method.

(In the general formulas (1) and (2), R _{1 to} R ₃ are each independently composed of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, and a phenyl group. One selected from the group, R _{1 to} R ₃ may have a substituent and may contain heteroatoms of O, N, P and S.
R ₄ is one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and hydrogen, and R ₄ has a substituent. It may contain heteroatoms of O, N, P and S.
R _{1 to} R ₄ may have an annular structure including each other. )

[2]
The method for producing a conjugated diene polymer according to the above [1], wherein R _{1 to} R ₃ are methyl groups in the general formula (1) and the general formula (2).
[3]
In the general formula (1) and the general formula (2),
The method for producing a conjugated diene polymer according to the above [1] or [2], wherein R ₄ is at least one selected from the group consisting of a methyl group, an ethyl group, a hydrogen group, and a phenyl group.
[4]
The method for producing a conjugated diene-based polymer according to any one of the above [1] to [3], wherein the polymerization initiator is an organolithium compound.
[5]
The conjugated diene-based weight according to any one of the above [1] to [4], further comprising a step of adding a coupling agent and coupling the conjugated diene-based polymer having an active terminal with the coupling agent. Manufacturing method of coalescence.
[6]
The conjugated diene polymer according to any one of [1] to [5], wherein the 1,2-vinyl bond content in the conjugated diene polymer is 10 mol% or more and 45 mol% or less. Production method.
[7]
The method for producing a conjugated diene polymer according to any one of [1] to [6] above, wherein the monomer conversion rate is 90% or more.
[8]
The method for producing a conjugated diene-based polymer according to any one of [1] to [7] above, wherein the polymerization temperature is 10 ° C. or higher and 80 ° C. or lower.
[9]
A step of producing a conjugated diene polymer by the method for producing a conjugated diene polymer according to any one of [1] to [8] above.
A step of mixing 0.5 parts by mass or more and 300 parts by mass or less of the silica-based inorganic filler with 100 parts by mass of the rubber component containing the conjugated diene polymer.
Have,
The rubber component contains 20% by mass or more of the conjugated diene polymer with respect to the total amount of the rubber component.
A method for producing a conjugated diene-based polymer composition.
[10]
The method for producing a conjugated diene-based polymer composition according to the above [9], further comprising a step of cross-linking the rubber component.
[11]
A step of producing a conjugated diene-based polymer composition by the method for producing a conjugated diene-based polymer composition according to the above [10], and
A step of molding a tire containing the conjugated diene polymer composition and
A method of manufacturing a tire.
[12]
A vinylizing agent composed of a polar compound used in the polymerization of conjugated diene compounds.
A vinylizing agent which is a compound represented by the following general formula (1) or general formula (2).

(In the general formulas (1) and (2), R _{1 to} R ₃ are each independently composed of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, and a phenyl group. One selected from the group, R _{1 to} R ₃ may have a substituent and may contain heteroatoms of O, N, P and S.
R ₄ is one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and hydrogen, and R ₄ has a substituent. It may contain heteroatoms of O, N, P and S.
R _{1 to} R ₄ may have an annular structure including each other. )

According to the present invention, a conjugated diene-based polymer having a high coupling reaction rate can be produced stably in a short reaction time with a high monomer conversion rate.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments, and the present invention is variously modified within the scope of the gist thereof. Can be carried out.

[Method for producing conjugated diene polymer]
The method for producing a conjugated diene polymer of the present embodiment is a conjugated diene system using a polymerization initiator in the presence of a polar compound represented by the following general formula (1) and / or general formula (2). It has a step of polymerizing a polymer.

(In the general formulas (1) and (2), R _{1 to} R ₃ are each independently composed of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, and a phenyl group. One selected from the group, R _{1 to} R ₃ may have a substituent and may contain heteroatoms of O, N, P and S.
R ₄ is one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and hydrogen, and R ₄ has a substituent. It may contain heteroatoms of O, N, P and S.
R _{1 to} R ₄ may have an annular structure including each other. )

By carrying out the polymerization step using a polar compound having a specific structure as described above, a conjugated diene-based polymer having a high coupling reaction rate can be obtained with a high monomer addition rate, a stable and short reaction time. Can be manufactured.

(Polymerization process)
In the method for producing a conjugated diene polymer of the present embodiment, it is preferable that the polymerization step of the conjugated diene polymer is a growth reaction by a living anionic polymerization reaction.

The polymerization reaction mode in the polymerization step is not limited to the following, and examples thereof include a batch type (also referred to as “batch type”) and a continuous type polymerization reaction mode.
As the batch reactor, for example, a tank type reactor with a stirrer is used. In batch formulas, preferably, the monomer, solvent, and polymerization initiator are first fed to the reactor, and if necessary, the monomers are added continuously or intermittently during the polymerization, within the reactor. A polymer solution containing the polymer is obtained, and the polymer solution is discharged after the completion of the polymerization.
In the continuous type, a plug-flow type reactor can be preferably used. In the continuous formula, preferably, the monomer, the solvent, and the polymerization initiator are continuously fed to the reactor to obtain a polymer solution containing the polymer in the reactor, and the polymer solution is continuously obtained. Is discharged.

Further, in the case of copolymerizing a conjugated diene compound and a vinyl aromatic compound as a monomer, as a method for randomizing them, for example, as described in JP-A-59-140211. , A method may be used in which the copolymerization reaction is started with the total amount of styrene and a part of 1,3-butadiene, and the remaining 1,3-butadiene is intermittently added during the copolymerization reaction.

In the present embodiment, if allenes, acetylenes, etc. are contained as impurities in the polymerization monomer or solvent of the conjugated diene compound or the like, the reaction of the reaction step described later may be hindered. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and further preferably 50 ppm or less.
Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethylacetylene and vinylacetylene.

In the present embodiment, the polymerization temperature in the reactor is preferably a temperature at which living anionic polymerization proceeds, and from the viewpoint of productivity, it is preferably 0 ° C. or higher and 120 ° C. or lower, and 10 ° C. or higher and 80 ° C. or lower. Is more preferable. In the above temperature range, particularly preferably in the temperature range of 10 ° C. or higher and 80 ° C. or lower, the living end of the conjugated diene polymer is less likely to be deactivated in the process of polymerization, and a conjugated diene polymer having a narrow molecular weight distribution can be obtained. There is a tendency. This is more preferable because the vulcanized product tends to have excellent mechanical strength and wear resistance. Further, when the coupling agent is reacted with the active terminal after the completion of the polymerization, it is more preferable because a conjugated diene-based polymer having a high coupling ratio tends to be obtained.
Further, in the present embodiment, the reaction time required for polymerization means the time from the time when the polymerization initiator is added until the polymerization temperature reaches the peak, and this reaction time is preferably short from the viewpoint of productivity. For example, when a reactor having an internal volume of 10 L is used, it is preferably within 20 minutes, more preferably within 15 minutes, and even more preferably within 10 minutes.

<Polar compound>
In the present embodiment, the polymerization step is carried out in the presence of the polar compound represented by the general formula (1) and / or the general formula (2), and the polar compound functions as a vinylizing agent.
As used herein, the term "vinyl agent" means a compound that can be coordinated to the terminal of a living anion. By coordinating the compound at the end of the living room, it becomes possible to control the 1,2-vinyl bond content of the conjugated diene-based polymer.
As the amount of the polar compound added is increased, the 1,2-vinyl bond content tends to increase. The 1,2-vinyl bond content with respect to the addition amount differs depending on the compound type to be added, because the coordination number and coordination form of each vinylizing agent per one living anion terminal are different.
Further, the polar compound is also effective in promoting the polymerization initiation reaction and the growth reaction, and the addition tends to shorten the polymerization reaction time and increase the polymerization conversion rate of the vinyl aromatic compound monomer. The degree of these effects also differs depending on the compound type to be added for the same reason as described above.

In this embodiment, at least one polar compound used as the vinylizing agent is selected from the general formula (1) and / or the general formula (2).

(In the general formulas (1) and (2), R _{1 to} R ₃ are each independently composed of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, and a phenyl group. One selected from the group, R _{1 to} R ₃ may have a substituent and may contain heteroatoms of O, N, P and S.
R ₄ is one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and hydrogen, and R ₄ has a substituent. It may contain heteroatoms of O, N, P and S.
R _{1 to} R ₄ may have an annular structure including each other. )

It is preferable that R _{1 to} R ₄ are not three-dimensionally bulky. This is because when the polar compound selected from the general formulas (1) and (2) is coordinated to the living anion terminal, the smaller the number of steric obstacles, the more the number of molecules of the polar compound coordinated per terminal. This is because the amount can be increased, which tends to reduce the 1,2-vinyl bond content in the conjugated diene-based polymer and increase the monomer conversion rate.
For example, with respect to the polar compound, it is preferable that R _{1 to} R ₃ of the compounds selected from the general formulas (1) and (2) are hydrocarbon groups having 1 carbon atom, specifically, methyl groups.
R ₄ is preferably any of a hydrocarbon having 1 to 2 carbon atoms, a hydrogen, a phenyl group, specifically, a methyl group, an ethyl group, hydrogen, and a phenyl group, and more preferably having 1 carbon atom. It is a hydrocarbon, or hydrogen, more preferably hydrogen.

The compound of the general formula (1) or the general formula (2) is not limited to the following, and is, for example, trimethyl orthoacetate, triethyl orthoacetate, triisopropyl orthodate, triphenyl orthoacetate, trimethyl orthoacetate, and the like. Triethyl orthoacetate, triisopropyl orthoacetate, triphenyl orthoacetate, trimethyl orthobutyrate, triethyl orthobutyrate, triisopropyl orthobutyrate, triphenyl orthobutyrate, trimethyl orthoisobutyrate, triethyl orthoisobutyrate, triisopropyl orthoisobutyrate, triphenyl orthobutyrate, Trimethyl orthopropionate, triethyl orthopropionate, triisopropyl orthopropionate, triphenyl orthopropionate, trimethyl orthoacetate, triethyl orthoacetate, triisopropyl orthoacetate, triphenyl orthoacetate, trimethyl orthoacetate, ortho Triethyl benzoate, triisopropyl ortho-benzoate, triphenyl ortho-benzoate, tetramethoxymethane, tetraethoxymethane, tetrapropoxymethane, 2-methoxy-1,3-dioxolane, 2-ethoxy-1,3-dioxolane, etc. Be done.

In the method for producing a conjugated diene polymer of the present embodiment, the amount of the polar compound used in the polymerization step, that is, the amount of the vinylizing agent used is not particularly limited, and depends on the desired 1,2-vinyl bond content and the like. Although it can be selected, when a reactor having an internal volume of 10 L or less is used, it is preferably 0.01 mol or more and 100 mol or less, and 2 mol or more and 40 mol or less is more preferable with respect to 1 mol of the polymerization initiator. preferable. When a reactor having an internal volume of 11 L or more and 99 L or less is used, it is preferably 0.01 mol or more and 100 mol or less, and more preferably 1 mol or more and 30 mol or less, with respect to 1 mol of the polymerization initiator. When a reactor having an internal volume of 100 L or more is used, it is preferably 0.01 mol or more and 100 mol or less, and more preferably 0.5 mol or more and 20 mol or less, with respect to 1 mol of the polymerization initiator.

Further, at least one polar compound selected from the general formula (1) and the general formula (2) can be used in combination with a compound that can be used as another vinylizing agent. In particular, the monomer conversion rate can be improved by combining the alkali metal alkoxide compound described later in an amount of 0.01 mol or more and 10 mol or less, more preferably 0.01 or more and 0.1 mol or less with respect to 1 mol of the polymerization initiator. This is preferable because the reaction time tends to be further shortened.

Other vinylizing agents include, but are not limited to, tertiary monoamines, such as trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1 , 1-Diethoxytriethylamine, N, N-dimethylformamide diisopropylacetal, N, N-dimethylformamide dicyclohexylacetal and the like.
Further, tertiary diamines can be used, for example, N, N, N', N'-tetramethyldiaminomethane, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-. Tetramethylpropanediamine, N, N, N', N'-tetramethyldiaminobutane, N, N, N', N'-tetramethyldiaminopentane, N, N, N', N'-tetramethylhexanediamine, Examples thereof include compounds such as dipiperidinopentane and dipiperidinoethane.
Further, chain ethers can be used, and examples thereof include dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.
Furthermore, cyclic ethers can be used, for example, tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, 2,2-bis. Examples thereof include compounds such as (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, and 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane.
Furthermore, alkali metal alkoxide compounds can be used, and examples thereof include compounds such as potassium-tert-amylate, potassium-tert-butyrate, sodium-tert-butyrate, and sodium amylate.

<Monomer that polymerizes conjugated diene-based polymer>
In the method for producing a conjugated diene polymer of the present embodiment, the conjugated diene polymer is polymerized in the presence of the above-mentioned polar compound in the polymerization step.
In the present specification, the "conjugated diene-based polymer" means a polymer containing a conjugated diene as a monomer unit, and includes a homopolymer and a copolymer.
From the viewpoint of facilitating the control of the vinyl bond content, the amount of conjugated diene in the polymer is preferably 40% by mass or more and 100% by mass or less, and more preferably 55% by mass or more and 88% by mass or less.
The conjugated diene-based polymer is obtained by polymerizing at least a conjugated diene compound, and if necessary, obtained by copolymerizing both a conjugated diene compound and a vinyl aromatic compound.

The conjugated diene compound is not limited to the following, but is, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3, Examples thereof include 3-pentadiene, 1,3-heptadiene and 1,3-hexadiene, with 1,3-butadiene and isoprene being particularly preferable, and 1,3-butadiene being more preferable. These may be used alone or in combination of two or more.

The vinyl aromatic compound is not limited to the following, and examples thereof include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like, and styrene is particularly used. preferable.
These may be used alone and copolymerized with the conjugated diene compound, or two or more thereof may be used in combination and copolymerized with the conjugated diene compound.

<Solvent>
When a solvent is used in the polymerization step of the method for producing a conjugated diene polymer of the present embodiment, the solvent is preferably a hydrocarbon solvent.
Examples of the hydrocarbon solvent include hexane, cyclohexane, and benzene.
By treating the impurities allenes and acetylenes with an organometallic compound before subjecting them to the polymerization reaction, a conjugated diene-based polymer having a high concentration of active terminals tends to be obtained, and the coupling ratio is high. It is preferable because a conjugated diene-based polymer tends to be obtained.

<Polymerization initiator>
In the method for producing a conjugated diene polymer of the present embodiment, an organolithium compound is preferable as the polymerization initiator used in the polymerization step.
The organolithium compound is not particularly limited as long as it can initiate the polymerization of the conjugated diene compound and the vinyl aromatic compound, and is not particularly limited to the following, but for example, n-butyllithium, sec-butyllithium, and tert-butyllithium. , N-propyllithium, iso-propyllithium, benzyllithium, piperidinolithium, pyrrolidinolithium and other monoorganolithium compounds; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1, Examples thereof include polyvalent lithium compounds such as 3,5-trilithiobenzene. Among these, n-butyllithium and sec-butyllithium are particularly preferable.

In addition to this, as the organic lithium compound, an alkyllithium compound having a substituted amino group or dialkylaminolithium can also be used. In this case, a conjugated diene-based polymer having a nitrogen atom, which is a component of an amino group, at the polymerization initiation terminal can be obtained.
The substituted amino group is an amino group having no active hydrogen or having a structure in which active hydrogen is protected. The alkyllithium compound having an amino group having no active hydrogen is not limited to the following, and includes, for example, 3-dimethylaminopropyl lithium, 3-diethylaminopropyl lithium, 4- (methylpropylamino) butyl lithium, and the like. Examples include 4-hexamethyleneiminobutyllithium.
Examples of the alkyllithium compound having an amino group having a structure in which active hydrogen is protected include, but are not limited to, 3-bistrimethylsilylaminopropyllithium and 4-trimethylsilylmethylaminobutyllithium.
The dialkylaminolithium is not limited to, for example, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithiumdi-n-hexylamide, lithium diheptylamide, lithium diisopropylamide, and lithium. Dioctylamide, lithium-di-2-ethylhexylamide, lithiumdidecylamide, lithiumethylpropylamide, lithiumethylbutylamide, lithiumethylbenzylamide, lithiummethylphenethylamide, lithiumhexamethyleneimide, lithiumpyrrolidide, lithiumpiperidi Do, lithium heptamethyleneimide, lithium morpholid, 1-lithioazacyclooctane, 6-lithio-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1-lithio-1,2 , 3,6-tetrahydropyridine.

These organolithium compounds having a substituted amino group can be used as an organolithium compound which is a solubilized oligomer by reacting a small amount of a polymerizable monomer such as a monomer such as 1,3-butadiene, isoprene, or styrene. It can also be used.

The amount of the organolithium compound used as the polymerization initiator is preferably determined by the molecular weight of the target conjugated diene polymer. The amount of a monomer such as a conjugated diene compound used with respect to the amount of the polymerization initiator used tends to be related to the degree of polymerization, that is, the number average molecular weight and the weight average molecular weight. Therefore, in order to increase the molecular weight of the conjugated diene polymer, it is preferable to adjust in the direction of decreasing the polymerization initiator, and in order to decrease the molecular weight, it is preferable to adjust in the direction of increasing the amount of the polymerization initiator.

(Coupling process)
In the method for producing a conjugated diene polymer of the present embodiment, a conjugated diene having an active end by a coupling agent is used from the viewpoint of improving the balance between workability and wear resistance, low hysteresis loss property and wet skid resistance. It is preferable to further have a step of coupling the system polymer.
By having the coupling step, it becomes easy to produce a polymer having a high molecular weight or to produce a polymer having a desired functional group. By using the polar compound represented by the above-mentioned general formula (1) or (2), a conjugated diene polymer having a high coupling reaction rate tends to be obtained.

<Coupling agent>
In the present specification, the "coupling agent" means a compound capable of reacting with an active terminal of a conjugated diene polymer to obtain a conjugated diene polymer containing a branched polymer component, and is reactive. From the viewpoint, it is preferable that the compound has one or more selected from the group consisting of an alkoxy group, an epoxy group, an ester group, and a halogen group.

The compound having an alkoxy group is not limited to the following, and for example, dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, and triethoxy. Methylsilane, 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- (triethoxy) Cyril) propyl] -3-methylhexahydropyrimidine, 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] tetrahydropyrimidine-1-yl} ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl ] -4- (trimethylsilyl) piperazine, 1- [3- (dimethoxymethylsilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (tributoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1 -[3- (Diethoxyethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [3- (dimethoxy) Methylsilyl) 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-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilyl) Pentil) -1-aza-2-silacycloheptan, 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.

The compound having an epoxy group is not limited to the following, and for example, 4,4'-diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine, diglycidylaniline, diglycidylluso. Examples thereof include toluidine, tetraglycidyl metaxylene diamine, tetraglycidyl aminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidyl aminomethylcyclohexane, and tetraglycidyl-1,3-bisaminomethylcyclohexane.

Examples of the compound having an ester group include, but are not limited to, methyl acetate ester, ethyl acetate ester, methyl adipate ester, ethyl adipate ester, methyl methacrylate ester, ethyl methacrylate ester and the like. Be done.

Compounds having a halogen group are not limited to the following, and include, for example, dimethyldichlorosilane, diethyldichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, tetrachlorosilane, dimethyldibromosilane, diethyldibromosilane, and methyltribromo. Examples include silane, ethyltribromosilane, and tetrabromosilane.

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

In the above-mentioned coupling agent, 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 of the polymerization initiator added, and 1.0 to 2.5. The range of doubling is more preferable, and the range of 1.0 to 2.0 times is further preferable.
When the total number of moles of the functional groups of the coupling agent with respect to the number of moles of the polymerization initiator added is within the range, silica is blended as a reinforcing filler and a vulcanized product is used as a sufficient coupling agent. Since the effect of the resulting functional group is obtained, the balance between the low hysteresis loss property and the wet skid resistance tends to be excellent. Further, within the above range, a copolymer containing a sufficient branched polymer component can be obtained, so that a vulcanized product having an excellent balance between wear resistance and processability tends to be obtained.

(Conjugated diene polymer)
The conjugated diene polymer obtained by the production method of the present embodiment preferably has a coupling ratio of 75% or more, preferably 85% or more, when the step of coupling with the above-mentioned coupling agent is included. More preferred. When the coupling ratio is within the above range, a copolymer containing a sufficient branched polymer component can be obtained, so that a vulcanized product having a better balance between wear resistance and processability can be obtained. It is in.
As a method for measuring the coupling rate, it can be obtained from the area ratio when measured by gel permeation chromatography (GPC) using a polystyrene-based gel column. Specifically, it can be measured by the method described in Examples described later.

The amount of conjugated diene in the conjugated diene-based polymer obtained by the production method of the present embodiment is not particularly limited, but is preferably 40% by mass or more and 100% by mass or less, and 55% by mass or more and 88% by mass or less. Is more preferable.
The amount of vinyl aromatic in the conjugated diene polymer obtained by the production method of the present embodiment is not particularly limited, but is preferably 0% by mass or more and 60% by mass or less, and is 12% by mass or more and 45% by mass or more. The following is more preferable.
When the amount of conjugated diene and the amount of vinyl aromatic are in the above ranges, the balance between low hysteresis loss property and wet skid resistance and wear resistance tend to be more excellent when the vulcanized product is used. Here, the amount of vinyl aromatic can be measured by the ultraviolet absorption of the phenyl group, and the amount of conjugated diene can also be obtained from this. Specifically, the measurement can be performed according to the method described in Examples described later.

<Monomer addition rate>
In the present specification, the conversion rate of the monomer indicates the average value of the conversion rate of all the monomers. Therefore, when the conjugated diene polymer is polybutadiene, it indicates the conversion rate of butadiene, and in the case of a copolymer with aromatic vinyl. Shows the average value of the conversion rate of aromatic vinyl and the conversion rate of conjugated diene.
The monomer conversion rate of the conjugated diene-based polymer obtained by the production method of the present embodiment is preferably 90% or more, more preferably 98% or more, from the viewpoint of improving productivity and randomness of the polymer. , More preferably 99% or more.
When the monomer conversion rate is less than 90%, there is a high possibility that a vinyl aromatic compound block is formed at the end of the polymer, which lowers the coupling rate and saves fuel consumption as a vulcanized product. It is not preferable because the fuel efficiency tends to decrease and the strength tends to decrease when the tire is used.
The monomer conversion rate can be measured according to the method described in Examples described later.
The monomer conversion rate of the conjugated diene polymer can be controlled within the above numerical range by using the polar compounds represented by the general formulas (1) and / or (2) in the polymerization step.

<Vinyl bond content>
The 1,2-vinyl bond content in the conjugated diene polymer obtained by the production method of the present embodiment is preferably 10 mol% or more and 45 mol% or less, and is 12 mol% or more and 35 mol% or less. More preferably, it is more preferably 15 mol% or more and 35 mol% or less.
When the 1,2-vinyl bond content is within the above range, a vulcanized product having a better balance between low hysteresis loss performance and wet skid resistance performance and also satisfying wear resistance tends to be obtained.
The 1,2-vinyl bond content in the conjugated diene polymer is controlled within the above numerical range by appropriately adjusting the amount of the conjugated diene compound as the polymerization monomer, the amount of the vinylizing agent added, the polymerization temperature, and the like. can do.

When the conjugated diene polymer obtained by the production method of the present embodiment is a copolymer of butadiene and styrene, the method of Hampton (RR Hampton, Analytical Chemistry, 21,923 (1949)) is used. , The 1,2-vinyl bond content in the butadiene bond unit can be determined. Specifically, it can be measured by the method described in Examples described later.

The amount of cis 1,4-bonding in the conjugated diene compound unit of the conjugated diene polymer obtained by the production method of the present embodiment is not particularly limited, but is preferably 8.0 mol% or more and 99 mol% or less. It is more preferably 20 mol% or more and 98 mol% or less, and further preferably 25 mol% or more and 90 mol% or less. By setting the cis 1,4-bonding amount in the above range, the rolling resistance characteristics tend to be better.

When the conjugated diene polymer obtained by the production method of the present embodiment is a random copolymer, the composition distribution of each monomer in the random copolymer chain is not particularly limited, and is, for example, statistically random. Examples thereof include a completely random copolymer having a composition close to the above, and a tapered (gradient) random copolymer having a tapered composition. The bonding mode of the conjugated diene, that is, the composition such as 1,4-bonding and 1,2-bonding, may be uniform or may be distributed.

The molecular weight of the conjugated diene-based polymer obtained by the production method of the present embodiment can be controlled, for example, by adjusting the amount of the organolithium compound used as the polymerization initiator as described above. Further, as for the molecular weight distribution of the conjugated diene polymer of the present embodiment, the residence time distribution may be adjusted in either the continuous type or the batch type polymerization mode. For example, when the residence time distribution is made small, that is, when the time distribution of the growth reaction is made narrow, the molecular weight distribution tends to be small. In the batch type, preferably, a method using a tank type reactor with a stirrer in which sufficient stirring is performed so that the composition in the reactor becomes uniform, and in a continuous type, a method using a tube type reactor having almost no backmix. preferable.

<Stabilizer>
In the method for producing a conjugated diene polymer of the present embodiment, it is preferable to add a stabilizer for rubber from the viewpoint of suppressing gel formation after polymerization and improving stability during processing.
The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT) and n-octadecyl-3- (4'-) can be used. Antioxidants such as hydroxy-3', 5'-di-tert-butylphenol) propionate and 2-methyl-4,6-bis [(octylthio) methyl] phenol are preferred.

<Extension oil>
Further, in the method for producing a conjugated diene-based polymer of the present embodiment, in order to further improve the processability of the conjugated diene-based polymer, extension oil can be further added as needed.
The method of adding the spreading oil to the conjugated diene-based copolymer is not particularly limited, but a method of adding the spreading oil to the polymer solution and mixing the mixture to obtain the spreading oil polymer solution is preferable.
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 bleeding, an aroma substitute oil having a polycyclic aromatic (PCA) component of 3.0% by mass or less according to the IP346 method is preferable.
Examples of the aroma substitute oil include TDAE (Treatd Distillate Aromatic Extracts) shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), MES (Mild Extraction Extract), and RA.
The content of the spreading oil is not particularly limited, but is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more and 37. parts by mass with respect to the total amount (100 parts by mass) of the conjugated diene polymer. It is 5 parts by mass or less.

<Recovery of conjugated diene polymer>
As a method for obtaining the conjugated diene polymer of the present embodiment from the 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 filtered off, and further dehydrated and dried to obtain the conjugated diene polymer. Concentrated in a flushing tank and further vent extruded. Examples include a method of devolatile with a machine or the like and a method of directly devolatile with a drum dryer or the like.

[Method for Producing Conjugated Diene Polymer Composition]
In the method for producing the conjugated diene polymer composition of the present embodiment, as described above, a polymerization initiator is used in the presence of the polar compound represented by the general formula (1) and / or the general formula (2). The step of polymerizing the conjugated diene compound and other polymerization monomers as needed to produce the conjugated diene polymer, and the conjugated diene polymer obtained by the polymerization step and, if necessary, other It has a step of mixing a silica-based inorganic filler of 0.5 parts by mass or more and 300 parts by mass or less with 100 parts by mass of a rubber component containing a component.
From the viewpoint of improving low temperature characteristics and wear resistance, the rubber component contains 20% by mass or more of the conjugated diene polymer obtained by the production method of the present embodiment with respect to the total amount (100% by mass) of the rubber component. It is preferably contained in an amount of 30% by mass or more, more preferably 35% by mass or more.

(Mixing process of silica-based inorganic filler)
The silica-based inorganic filler mixed with the conjugated diene-based polymer refers to solid particles containing the chemical formula SiO ₂ or Si ₃ Al as the main component, for example, silica, clay, talc, mica, diatomaceous earth. , Inorganic fibrous substances such as wollastonite, montmorillonite, zeolite, and glass fiber.
Further, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica-based inorganic filler can also be used. In particular, silica and glass fiber are preferable.
As the silica, dry method white carbon, wet method white carbon, synthetic silicate-based white carbon, colloidal silica and the like can be used. These preferably have an average particle size of 0.01 μm or more and 150 μm or less.
Further, in the production method of the present embodiment, in order to disperse the silica-based inorganic filler in the conjugated diene-based polymer composition and sufficiently exert the effect of adding silica, the average dispersed particles of the silica-based inorganic filler are dispersed. The diameter is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.05 μm or more and 0.5 μm or less.

The blending amount of the silica-based inorganic filler in the method for producing the conjugated diene-based polymer composition of the present embodiment is 100 parts by mass of the rubber component containing the conjugated diene-based polymer obtained by the above-mentioned production method of the present embodiment. It is 0.5 parts by mass or more and 300 parts by mass or less, preferably 5.0 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 120 parts by mass or less.
When the blending 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 blending amount is 300 parts by mass or less, in the conjugated diene-based polymer. The dispersibility of the silica-based inorganic filler becomes good, and excellent processability and high mechanical strength can be obtained.

In the present embodiment, the method of 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 mixer such as an open roll, a Banbury mixer, a kneader, a single-screw screw extruder, a twin-screw screw extruder, or a multi-screw screw extruder, after melting and mixing each component, and a solvent. There is a method of heating and removing the solvent. Among these, a melt-kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferable from the viewpoint of productivity and good kneading.
Further, the rubber component and the silica-based inorganic filler may be kneaded in total amounts at the same time, or each may be kneaded in a plurality of times.

(Vulcanization process using vulcanizing agent)
In the method for producing a conjugated diene-based polymer composition of the present embodiment, a vulcanization step may be carried out using a vulcanizing agent. It is known that the rubber component is crosslinked by a vulcanization step to develop tough rubber elasticity. In the vulcanization step, the rubber component can be crosslinked by means such as heat treatment.
As the sulfide agent, for example, a radical generator such as an organic peroxide and an azo compound, an oxime compound, a nitroso compound, a polyamine compound, sulfur, and a sulfur compound can be used. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, high molecular weight polysulfur compounds and the like.
The amount of the vulcanizing agent used is not particularly limited, but is 0.01 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component containing the conjugated diene polymer obtained by the production method of the present embodiment. It is preferable, and more preferably 0.1 parts by mass or more and 15 parts by mass or less.

A vulcanization accelerator may be further used during vulcanization.
Examples of the vulcanization accelerator include sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, and dithiocarbamate-based ones.
Further, in vulcanization, a vulcanization aid may be further used. Examples of the vulcanization aid include zinc oxide and stearic acid.
The amount of these vulcanization accelerators and / or vulcanization aids used is 0.01 part by mass or more and 20 parts by mass with respect to 100 parts by mass of the rubber component containing the conjugated diene polymer obtained by the production method of the present embodiment. It is preferably 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less.

(Combining a softener for rubber)
In the method for producing a conjugated diene-based polymer composition of the present embodiment, a step of further blending a softening agent for rubber may be carried out in order to improve processability.
As the softening agent for rubber, for example, mineral oil and liquid or low molecular weight synthetic softening agent are preferable.
A softening agent for mineral oil-based rubber called process oil or extender oil, which is generally used for the purpose of softening, increasing volume, improving processability, etc. of rubber components, is a mixture of aromatic ring, naphthen ring, and paraffin chain, and is paraffin. A chain having 50% or more of carbon atoms in the chain is called paraffin-based, a chain having a naphthen ring carbon number of 30 to 45% in total carbon is naphthen-based, and an aromatic carbon number is 30% in total carbon. Those that exceed are called aromatics.
As the softening agent for rubber used in the method for producing the conjugated diene-based polymer composition of the present embodiment, naphthenic and / or paraffin-based ones are preferable.
As the synthetic softener, for example, polybutene, low molecular weight polybutadiene and the like can be used, but the softener for mineral oil-based rubber gives better results.

In the method for producing the conjugated diene polymer composition of the present embodiment, when the softening agent for rubber is blended, the blending amount of the softening agent for rubber is the same as that of the conjugated diene polymer obtained by the manufacturing method of the present embodiment. It is preferably 0 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 90 parts by mass or less, and further preferably 30 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the rubber component contained. is there.
When the blending amount of the softening agent for rubber is within the above range, the processability becomes good, bleed-out can be suppressed, and the occurrence of stickiness on the surface tends to be suppressed.

(Rubber component other than conjugated diene polymer)
In the method for producing a conjugated diene-based polymer composition of the present embodiment, as a rubber component, a rubber-like polymer other than the conjugated diene-based polymer obtained by the above-mentioned production method of the present embodiment is used as the above-mentioned conjugated diene-based polymer. It can be used in combination with a polymer.
Examples of such a rubber-like polymer include 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 a natural polymer. Rubber is mentioned.
Specifically, butadiene rubber or its hydrogen additive, isoprene rubber or its hydrogen additive, styrene-butadiene rubber or its hydrogen additive, styrene-butadiene block copolymer or its hydrogen additive, styrene-isoprene block copolymer weight. Examples thereof include styrene-based elastomers such as coalescing or hydrogenated products thereof, and acrylonitrile-butadiene rubber or hydrogenated products thereof.
Examples of the non-diene polymer include olefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethien-hexene rubber, and ethylene-octene rubber, butyl rubber, and brominated butyl rubber. Examples thereof include acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, and polysulfide rubber.
These rubber-like polymers may be rubbers to which functional groups have been added.
These may be used alone or in combination of two or more.

When the rubber-like polymer obtained by the production method of the present embodiment is combined with the various rubber-like polymers described above to obtain a rubber component, the rubber-like polymer is the conjugated diene-based polymer obtained by the production method of the present embodiment. It is preferably 1.0 part by mass or more and 400 parts by mass or less, more preferably 5.0 parts by mass or more and 200 parts by mass or less, and further preferably 10 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the polymer. It is less than a part.

(Mixing of additives)
In the method for producing a conjugated diene-based polymer composition of the present embodiment, various additives can be blended as necessary within a range that does not impair the effects of the present invention.
Additives include, for example, softeners, heat-resistant stabilizers, antistatic agents, weather-resistant stabilizers, anti-aging agents, fillers, colorants, and lubricants.
Examples of the softening agent that can be blended as needed for adjusting the hardness and fluidity of the product using the conjugated diene-based polymer composition 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-resistant stabilizer, antistatic agent, weather-resistant stabilizer, anti-aging agent, colorant, and lubricant.

[Tire manufacturing method]
The method for producing a tire of the present embodiment includes a step of molding a tire containing the conjugated diene-based polymer composition obtained by the method for producing the present embodiment.
For tires using the conjugated diene rubber polymer composition, for example, a rubber component, a silica-based inorganic filler, carbon black, sulfur, natural rubber, and various compounding agents are kneaded to form a plate, and then the desired portion is formed. It is manufactured by molding it into a suitable shape and then heating and pressurizing it to cause a chemical reaction to vulcanize it.
The conjugated diene-based polymer composition of the present embodiment can be molded into anti-vibration rubber and various industrial products in addition to tires.

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples.
Various physical properties in Examples and Comparative Examples were measured by the methods shown below.

(Physical properties 1) Monomer conversion rate Add 0.5 g of normal propylbenzene (nPB) and 20 g of toluene to a pressure-resistant glass bottle, and sample 20 g of the solution in the reactor 1 minute after the polymerization temperature peak in a sample container with a rubber stopper and a crown. did.
3 μL of the solution in the pressure-resistant bottle was measured by a gas chromatography (GC) apparatus under the following conditions.

GC measurement conditions:
GC equipment: "GC-2014S" manufactured by Shimadzu Corporation
Column: Shimadzu Corporation, glass column with filler, inner diameter 3.2 mm, diameter 5.1 m
Apiezon GREASE L 15% UniportB mesh 60/80 filler
Aging carrier gas: nitrogen, 50 mL / min
Hydrogen gas: 0.6 kg / cm ³
Air gas: 0.5 kg / cm ³
Measurement temperature: 90 ° C to 150 ° C
Temperature rise rate: 16 ° C / min Injection temperature: 200 ° C
Detection temperature: 190 ° C
Driving amount: 3 μL

The monomer conversion rate (%) in the reactor was calculated by the following calculation method.

Monomer conversion rate (%) = [Conversion rate of butadiene monomer (%) + Conversion rate of styrene monomer (%)] / 2

The conversion rate (%) of each monomer in the above formula was calculated by the following method.

Butadiene monomer conversion rate (%) = 100-{[butadiene peak area area x nPB amount in sample solution x 10 ⁶ ] / [sampling solution amount (g) x monomer concentration in reactor (%) x in monomer Butadiene ratio (%) x nPB area area]}

Styrene monomer conversion rate (%) = 100-{[Styrene peak area area x amount of nPB in sample solution x 10 ⁶ ] / [sample solution amount (g) x monomer concentration in reactor (%) x in monomer Styrene ratio (%) x nPB area area]}

(Physical properties 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 of 600 to 1000 cm is obtained by a single reflection ATR method (attenuated total reflection method) using FT-IR "Spectrem 100" manufactured by Perkin Elmer Japan. The microstructure (mol%) of the butadiene portion was determined according to the calculation formula of the Hampton method by measuring in the range of ^-1 and using the absorbance at a predetermined wave number.

(Physical properties 3) Molecular weight distribution, coupling rate Using gel permeation chromatography (GPC) using a conjugated diene polymer as a sample and connecting three of the following columns using polystyrene gel as a filler. The chromatogram was measured, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained by a calibration line using standard polystyrene, the molecular weight distribution (Mw / Mn) was calculated, and a molecular weight distribution curve was created.
From the prepared molecular weight distribution curve, the total peak area was set to 100, and the area excluding the peak area of the non-coupling polymer that was not coupled by the coupling agent from the total peak area was defined as the coupling rate (%).
Other measurement conditions were as follows.
Eluent: tetrahydrofuran (THF)
Guard column: Tosoh's "TSKguardcolum HHR-H"
Column: Tosoh's "TSKgel G6000HHR",
"TSKgel G5000HHR",
"TSKgel G4000HHR"
Oven temperature: 40 ° C
THF flow rate: 1.0 mL / min RI detector: "HLC8020" manufactured by Tosoh Corporation
Sample: 10 mg of conjugated diene polymer with respect to 20 mL of tetrahydrofuran (THF)
Inject 200 μL of dissolved product

<Example 1>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 19.5 g of trimethyl orthoformate (referred to as "Compound 1" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and 5 at a temperature condition of 75 ° C. A minute coupling reaction was performed.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample A) was obtained.
Table 1 shows the details of the polymerization conditions of Sample A, and the physical properties and evaluation results obtained by analysis.

<Example 2>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 5.88 g of trimethyl orthoacetate (referred to as "Compound 2" in the table) were added to the reactor under a nitrogen atmosphere. The mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 75 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample B) was obtained.
Table 1 shows the details of the polymerization conditions of Sample B, and the physical properties and evaluation results obtained by analysis.

<Example 3>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Reaction of 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 5.74 g of trimethyl orthopropionic acid (referred to as "Compound 3" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was placed in a vessel and the mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 77 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 77 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample C) was obtained.
Table 1 shows the details of the polymerization conditions of Sample C, and the physical properties and evaluation results obtained by analysis.

<Example 4>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Reaction of 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 4.46 g of trimethyl orthobenzoate (referred to as "Compound 4" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was placed in a vessel and the mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 76 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 76 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample D) was obtained.
Table 1 shows the details of the polymerization conditions of Sample D, and the physical properties and evaluation results obtained by analysis.

<Example 5>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 10.9 g of triethyl orthoformate (referred to as "Compound 5" in the table) were added to the reactor under a nitrogen atmosphere. The mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 75 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample E) was obtained.
Table 1 shows the details of the polymerization conditions of Sample E, and the physical properties and evaluation results obtained by analysis.

<Example 6>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane from which impurities have been removed in advance, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 26.0 g of trimethyl orthoformate (referred to as "Compound 1" in the table) in a nitrogen atmosphere. The mixture was heated to 48 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 74 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 74 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample F) was obtained.
Table 1 shows the details of the polymerization conditions of Sample F, and the physical properties and evaluation results obtained by analysis.

<Example 7>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 39.0 g of trimethyl orthoformate (referred to as "Compound 1" in the table) were added to the reactor under a nitrogen atmosphere. The mixture was heated to 46 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 73 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 73 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample G) was obtained.
Table 1 shows the details of the polymerization conditions of Sample G, and the physical properties and evaluation results obtained by analysis.

<Example 8>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 1.30 g of trimethyl orthoformate (referred to as "Compound 1" in the table) were added to the reactor under a nitrogen atmosphere. The mixture was heated to 57 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 79 ° C. One minute after the peak temperature, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane (denoted as "Cup-1" in the table) was added to the reactor. 0.42 g was added, and a coupling reaction was carried out for 5 minutes under a temperature condition of 79 ° C.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample H) was obtained.
Table 1 shows the details of the polymerization conditions of Sample H, and the physical properties and evaluation results obtained by analysis.

<Example 9>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 19.5 g of trimethyl orthoformate (referred to as "Compound 1" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 79 ° C.
One minute after the peak temperature, 0.25 g of methanol was added to the reactor to terminate the reaction. 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample I) was obtained.
Table 1 shows the details of the polymerization conditions of Sample I, and the physical properties and evaluation results obtained by analysis.

<Example 10>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.13 kg of styrene, 0.68 kg of 1,3 butadiene, and 19.5 g of trimethyl orthoformate (referred to as "Compound 1" in the table) were placed in a reactor under a nitrogen atmosphere. The mixture was charged and the mixture was heated to 57 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 82 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 82 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample J) was obtained.
Table 1 shows the details of the polymerization conditions of Sample J, and the physical properties and evaluation results obtained by analysis.

<Example 11>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.81 kg of 1,3 butadiene, and 19.5 g of trimethyl orthoformate (referred to as "Compound 1" in the table) were charged into a reactor under a nitrogen atmosphere, and the mixture was prepared. It was heated to 51 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 78 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 78 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample K) was obtained.
Table 1 shows the details of the sample K polymerization conditions, and the physical properties and evaluation results obtained by analysis.

<Comparative example 1>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Cyclohexane 5.6 kg, styrene 0.13 kg, 1,3-butadiene 0.68 kg, 2,2-bis (2-oxolanyl) propane (referred to as "Compound 6" in the table) 0.113 g Was charged into a reactor under a nitrogen atmosphere, and the mixture was heated to 54 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 75 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample L) was obtained.
Table 1 shows the details of the polymerization conditions of Sample L, and the physical properties and evaluation results obtained by analysis.

<Comparative example 2>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Cyclohexane 5.6 kg, styrene 0.13 kg, 1,3-butadiene 0.68 kg, 2,2-bis (2-oxolanyl) propane (referred to as "Compound 6" in the table) 0.146 g Was charged into a reactor under a nitrogen atmosphere, and the mixture was heated to 58 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 87 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 87 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample M) was obtained.
Table 1 shows the details of the polymerization conditions of Sample M, and the physical properties and evaluation results obtained by analysis.

<Comparative example 3>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Cyclohexane 5.6 kg, styrene 0.13 kg, 1,3-butadiene 0.68 kg, 2,2-bis (2-oxolanyl) propane (denoted as "Compound 6" in the table) 0.338 g Was charged into a reactor under a nitrogen atmosphere, and the mixture was heated to 49 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 75 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample N) was obtained.
Table 1 shows the details of the polymerization conditions of Sample N, and the physical properties and evaluation results obtained by analysis.

<Comparative example 4>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Cyclohexane 5.6 kg, styrene 0.13 kg, 1,3-butadiene 0.68 kg, 2,2-bis (2-oxolanyl) propane (denoted as "Compound 6" in the table) 0.878 g Was charged into a reactor under a nitrogen atmosphere, and the mixture was heated to 52 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 75 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample O) was obtained.
Table 1 shows the details of the polymerization conditions of Sample O, and the physical properties and evaluation results obtained by analysis.

<Comparative example 5>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Cyclohexane 5.6 kg, styrene 0.13 kg, 1,3-butadiene 0.68 kg, 2,2-bis (2-oxolanyl) propane (denoted as "Compound 6" in the table) 0.068 g Was charged into a reactor under a nitrogen atmosphere, and the mixture was heated to 58 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 71 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 71 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample P) was obtained.
Table 1 shows the details of the polymerization conditions of Sample P, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 6>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
Cyclohexane 5.6 kg, styrene 0.13 kg, 1,3-butadiene 0.68 kg, 2,2-bis (2-oxolanyl) propane (referred to as "Compound 6" in the table) 0.113 g Was charged into a reactor under a nitrogen atmosphere, and the mixture was heated to 54 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.25 g of methanol was added to the reactor to terminate the reaction.
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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample Q) was obtained.
Table 1 shows the details of the polymerization conditions of Sample Q, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 7>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
5.6 kg of cyclohexane from which impurities have been removed in advance, 0.81 kg of 1,3-butadiene, and 0.113 g of 2,2-bis (2-oxolanyl) propane (referred to as "Compound 6" in the table) were added under a nitrogen atmosphere. The mixture was charged in a reactor and heated to 52 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 76 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 76 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample R) was obtained.
Table 1 shows the details of the polymerization conditions of Sample R, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 8>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 0.25 g of tetramethylenediamine (referred to as "Compound 7" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 50 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 78 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 78 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample S) was obtained.
Table 1 shows the details of the polymerization conditions of Sample S, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 9>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 0.25 g of tetramethylenediamine (referred to as "Compound 7" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 53 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 84 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 84 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample T) was obtained.
Table 1 shows the details of the polymerization conditions of Sample T, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 10>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 0.46 g of tetramethylenediamine (referred to as "Compound 7" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 52.0 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 75 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 75 ° C. A coupling reaction was carried out for 5 minutes.
The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample U) was obtained.
Table 1 shows the details of the polymerization conditions of Sample U, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 11>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 0.25 g of tetramethylenediamine (referred to as "Compound 7" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 50 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 79 ° C.
One minute after the peak temperature, 0.42 g of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor at a temperature condition of 79 ° C. A coupling reaction was carried out for 5 minutes. The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample V) was obtained.
Table 1 shows the details of the polymerization conditions of Sample V, and the physical properties and evaluation results obtained by analysis.

<Comparative Example 12>
A temperature-controllable autoclave with an internal volume of 10 liters and a stirrer and jacket was used as the reactor.
A reactor with 5.6 kg of cyclohexane, 0.13 kg of styrene, 0.68 kg of 1,3-butadiene, and 0.25 g of tetramethylenediamine (referred to as "Compound 7" in the table) from which impurities have been removed in advance under a nitrogen atmosphere. The mixture was heated to 48 ° 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 6.12 mmol, and the reaction was started.
The peak temperature in the final reactor reached 79 ° C.
One minute after the peak temperature, 0.25 g of methanol was added to the reactor to terminate the reaction. The reaction was terminated by adding 0.25 g of methanol to this 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 the polymer is dried by a dryer. , A styrene-butadiene copolymer having a modified component (Sample W) was obtained.
Table 1 shows the details of the polymerization conditions of Sample W, and the physical properties and evaluation results obtained by analysis.

The method for producing a conjugated diene polymer of the present invention is industrially applicable in the field of manufacturing technology for materials such as automobile interior / exterior parts, anti-vibration rubber, belts, footwear, foams, various industrial parts, and tire applications. May be available.

Claims (12)

A conjugated diene polymer having a step of polymerizing a conjugated diene polymer using a polymerization initiator in the presence of a polar compound represented by the following general formula (1) and / or general formula (2). Production method.
(In the general formulas (1) and (2), R _{1 to} R ₃ are each independently composed of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, and a phenyl group. One selected from the group, R _{1 to} R ₃ may have a substituent and may contain heteroatoms of O, N, P and S.
R ₄ is one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and hydrogen, and R ₄ has a substituent. It may contain heteroatoms of O, N, P and S.
R _{1 to} R ₄ may have an annular structure including each other. ) In the general formula (1) and the general formula (2), R _{1 to} R ₃ are methyl groups.
The method for producing a conjugated diene polymer according to claim 1. In the general formula (1) and the general formula (2),
R ₄ is at least one selected from the group consisting of a methyl group, an ethyl group, a hydrogen group, and a phenyl group.
The method for producing a conjugated diene polymer according to claim 1 or 2. The polymerization initiator is an organolithium compound.
The method for producing a conjugated diene polymer according to any one of claims 1 to 3. Further comprising a step of adding a coupling agent and coupling the conjugated diene-based polymer having an active terminal with the coupling agent.
The method for producing a conjugated diene polymer according to any one of claims 1 to 4. The 1,2-vinyl bond content in the conjugated diene polymer is 10 mol% or more and 45 mol% or less.
The method for producing a conjugated diene polymer according to any one of claims 1 to 5. The method for producing a conjugated diene polymer according to any one of claims 1 to 6, wherein the monomer conversion rate is 90% or more. The polymerization temperature is 10 ° C or higher and 80 ° C or lower.
The method for producing a conjugated diene polymer according to any one of claims 1 to 7. A step of producing a conjugated diene polymer by the method for producing a conjugated diene polymer according to any one of claims 1 to 8.
A step of mixing 0.5 parts by mass or more and 300 parts by mass or less of the silica-based inorganic filler with 100 parts by mass of the rubber component containing the conjugated diene polymer.
Have,
The rubber component contains 20% by mass or more of the conjugated diene polymer with respect to the total amount of the rubber component.
A method for producing a conjugated diene-based polymer composition. The method for producing a conjugated diene-based polymer composition according to claim 9, further comprising a step of cross-linking the rubber component. A step of producing a conjugated diene-based polymer composition by the method for producing a conjugated diene-based polymer composition according to claim 10.
A step of molding a tire containing the conjugated diene polymer composition and
A method of manufacturing a tire. A vinylizing agent composed of a polar compound used in the polymerization of conjugated diene compounds.
A vinylizing agent which is a compound represented by the following general formula (1) or general formula (2).
(In the general formulas (1) and (2), R _{1 to} R ₃ are each independently composed of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, and a phenyl group. One selected from the group, R _{1 to} R ₃ may have a substituent and may contain heteroatoms of O, N, P and S.
R ₄ is one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a cyclic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and hydrogen, and R ₄ has a substituent. It may contain heteroatoms of O, N, P and S.
R _{1 to} R ₄ may have an annular structure including each other. )