KR20180065931A - Modified conjugated diene polymer, modified conjugated diene polymer composition and tire - Google Patents

Abstract

A modified conjugated diene polymer having good fracture properties at a high temperature can be obtained as a vulcanized product. The modified conjugated diene polymer of the present invention has the mooney stress relaxation rate of 0.45 or more at 110°C; the modification ratio of 75 mass% or more; the weight average molecular weight (Mw) of 200,000 or more and 3,000,000 or less; and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.5 or more and 3.5 or less.

Description

MODIFIED CONJUGATED DIENE POLYMER, MODIFIED CONJUGATED DIENE POLYMER COMPOSITION AND TIRE, AND MODIFIED CONJUGATED DIENE POLYMER,

The present invention relates to a modified conjugated diene polymer, a modified conjugated diene polymer composition, and a tire.

In recent years, from the viewpoints of resource conservation and environmental measures, the demand for low fuel consumption of tires is increasing, and low heat generation and low fuel consumption (low hysteresis) of tires are emphasized.

In order to improve the low hysteresis property, it is general to lower the rolling resistance by using a rubber composition having a low exothermicity.

As a rubber composition corresponding to such a demand, there is a rubber composition using silica as a reinforcing filler contained in the rubber composition, and it is known that the balance between low heat build-up and brake performance (wet skid resistance) on a wet road surface is excellent.

However, silica having a hydrophilic surface has a problem in that, in a composition obtained by mixing with a conjugated diene rubber having a high hydrophobicity, the particles are aggregated with each other and the dispersibility is not good. Therefore, by introducing a functional group interacting with the surface of the silica to the conjugated diene rubber to improve the affinity with the surface of the silica and improve the dispersibility of the silica in the rubber composition, it is desired to have a low hysteresis property Attempts are being made.

For example, Patent Documents 1 and 2 disclose modified diene conjugated rubbers obtained by reacting an alkoxysilane containing an amino group at the terminal of a polymer, and compositions of these and silica.

Patent Document 3 discloses a modified conjugated diene rubber obtained by initiating polymerization using an initiator containing an amino group and reacting an alkoxysilane containing an amino group at the terminal of the polymer.

Japanese Patent Application Laid-Open No. 2004-18795 Korean Patent Publication No. 2016-0063227 U.S. Patent Application Publication No. 2016/0159957

BACKGROUND ART [0002] As automobiles become more sophisticated, there is a growing demand for high performance tires with high performance, especially for high-speed conditions.

When the automobile travels at a high speed, the tire is exposed to high temperatures due to the generation of frictional heat. Therefore, development of a rubber composition which is excellent in fracture characteristics at high temperatures as a rubber material constituting such a tire is particularly required.

However, although tires using the rubber compositions disclosed in the above-mentioned Patent Documents 1 to 3 exhibit the effect of low heat generation, the automobile tires for high-speed driving have a problem that the fracture characteristics at high temperatures are not sufficient yet have.

Thus, in the present invention, in view of the problems of the prior art described above, it is an object of the present invention to provide a modified conjugated diene polymer which is excellent in fracture characteristics at a high temperature when made into a vulcanized product.

Means for Solving the Problems The present inventors have made intensive investigations in order to solve the problems of the prior art described above. As a result, they have found that when the mooney relaxation ratio at 110 ° C is not less than a predetermined value, the modifying ratio is not less than a predetermined value, , And that the modified conjugated diene polymer having a molecular weight distribution within a predetermined range has a fracture property at a satisfactory high temperature when it is made into a vulcanized product, thereby completing the present invention.

That is, the present invention is as follows.

[1] a mooney relaxation ratio at 110 ° C of at least 0.45,

A modification ratio of not less than 75% by mass,

Has a weight average molecular weight (Mw) of 200,000 or more and 3,000,000 or less,

(Weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.5 or more and 3.5 or less,

Modified conjugated diene polymer.

[2] The modified conjugated diene polymer according to [1], wherein the content of nitrogen atoms is 25 mass ppm or more based on the total amount of the modified conjugated diene polymer.

[3] The modified conjugated diene polymer according to [1] or [2], which is represented by the following general formula (A) or (B)

(In the general formula (A), R ²¹ to R ²⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ each independently represent an alkyl group having 1 to 20 carbon atoms A, b, c, and d are as defined above for (a + b) and (a + b), and R ²⁷ represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. a and c each represent an integer of 1 or 2, and b and d represent an integer of 0 or 1, and (Polym) represents a conjugated diene-based polymer as long as the (c + d) And at least one terminal thereof is a functional group represented by any one of the following general formulas (1) to (4): R ²¹ and R ^{23 in the} presence of a plurality of residues, and a plurality of residues (Polym) It may be different or it may be different)

(In the general formula (B), each of R ²⁸ to R ³³ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁴ to R ³⁶ each independently represent an alkyl group having 1 to 20 carbon atoms A, b, c, d, e, and f are as long as a, c, and e are as long as each of (a + b), (c + d), and B, d and f each independently represent an integer of 0 or 1. (Polym) represents a conjugated diene-based polymer, and at least one terminal thereof is represented by the following general formula (1) (4). When there are a plurality of R ²⁸ , R ^30, and R ³² , and the plurality of (Polym) present are independent of one another, they may be the same or different.

(In the general formula (1), R ¹⁰ and R ¹¹ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, R ¹⁰ and R ¹¹ may combine to form a cyclic structure together with the adjacent nitrogen atom, and in this case, R ¹⁰ and R ^{11 each} represent an alkyl group having 5 to 12 carbon atoms, and an unsaturated bond or a And the protecting group may be an alkyl-substituted silyl group.

(In the general formula (2), R ¹² and R ¹³ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, One species.

R ¹² and R ¹³ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ¹² and R ¹³ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure being.

The protecting group is an alkyl-substituted silyl group.

R ¹⁴ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent or a conjugated diene polymer chain having 1 to 20 carbon atoms)

(In the general formula (3), R ¹⁵ and R ¹⁶ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 20 carbon atoms, One species.

R ¹⁵ and R ¹⁶ may combine with each other to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ¹⁵ and R ¹⁶ represent an alkyl group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof. Also, the protecting group is an alkyl-substituted silyl group)

(In the general formula (4), R ¹⁷ represents a hydrocarbon group having 2 to 10 carbon atoms and may have an unsaturated bond or branch structure in a part thereof. R ¹⁸ represents an alkyl group having 1 to 12 carbon atoms or a protecting group, And the protecting group may be an alkyl-substituted silyl group.

[4] The modified conjugated diene polymer according to any one of [1] to [3], wherein the moonic relaxation ratio at 110 ° C is less than 0.60.

[5] The modified conjugated diene-based polymer according to any one of [1] to [3], wherein the moonic relaxation rate at 110 ° C is 0.60 or more and 0.80 or less.

[6] The modified conjugated diene polymer according to any one of [1] to [5], wherein the modification ratio is 95% by mass or less.

[7] The modified conjugated diene polymer according to any one of [1] to [6], wherein the amount of vinyl bond in the conjugated diene bonding unit is 30 mol% or more.

[8] A rubber composition,

A filler in an amount of 5.0 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the rubber component,

The rubber component preferably contains 10% by mass or more of the modified conjugated diene polymer according to any one of [1] to [7], based on the total amount of the rubber component.

Modified conjugated diene-based polymer composition.

[9] The modified conjugated diene-based polymer composition according to the above-mentioned [8], wherein the rubber component comprises 10 mass% or more of a natural rubber based on the total amount of the rubber component.

[10] A tire comprising the modified conjugated diene-based polymer composition according to the above [8] or [9].

According to the present invention, a modified conjugated diene polymer having a fracture property at a high temperature when vulcanized is obtained can be obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as " present embodiment ") will be described in detail.

The following embodiments are illustrative of the present invention and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist of the invention.

[Modified conjugated diene polymer]

The modified conjugated diene polymer of the present embodiment,

A moonbeam relaxation rate at 110 DEG C of 0.45 or more,

A modification ratio of not less than 75% by mass,

Has a weight average molecular weight (Mw) of 200,000 or more and 3,000,000 or less,

(Weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.5 or more and 3.5 or less.

The modified conjugated diene polymer of the present embodiment has a Mooney moderation rate of 0.45 or more measured at 110 캜, that is, at a temperature of 110 캜, from the viewpoint of breaking strength at high temperatures.

Hereinafter, it is simply referred to as " Mooney Relaxation Rate " or " MSR ".

The mooney relaxation rate is an index of molecular entanglement of the modified conjugated diene-based copolymer, and the lower the degree, the larger the entanglement of the molecules, and becomes an index of the branch structure and the molecular weight.

The modified conjugated diene polymer having an MSR of 0.45 or more tends to be excellent in fracture characteristics under high temperature when it is made into a vulcanized product.

The upper limit of the MSR is not particularly limited, but is preferably 0.80 or less. The modified conjugated diene polymer having an MSR in the range of from 0.45 or more to less than 0.60 has a low Mooney viscosity when it is made into a vulcanized product and tends to have excellent processability.

The modified conjugated diene polymer having an MSR in the range of 0.60 or more and 0.80 or less tends to have better fracture toughness in a wider temperature range than that of a vulcanized product.

From the viewpoint of fracture characteristics at high temperatures and workability at the time of vulcanization, the MSR is more preferably 0.46 or more and 0.75 or less, and still more preferably 0.48 or more and 0.70.

The MSR of the modified conjugated diene polymer is an index of the molecular weight and the minute index of the modified conjugated diene polymer.

For example, as the MSR increases, the molecular weight and minute index of the denatured conjugated diene polymer (for example, the minute index of star-shaped polymer (also referred to as " number of arms of molded polymer & . In the case of comparing the denatured conjugated diene polymer having the same Mooney viscosity as described later, the MSR becomes larger as the branch of the modified conjugated diene polymer becomes smaller, so that the MSR in this case can be used as an index of the molecular index.

The MSR is measured using a Mooney viscometer as follows.

In the present embodiment, the temperature at which the moon-yard relaxation rate is measured is 110 占 폚. First, the sample is preheated for 1 minute, and then the rotor is rotated at 2 rpm. Torque after 4 minutes is measured, and the measured value is defined as Mooney viscosity (ML _{(1 + 4)} ). Thereafter, the rotation of the rotor was immediately stopped, the torque was recorded every 0.1 seconds for 1.6 seconds to 5 seconds after the stop, and the slope of the straight line when the torque and the time (seconds) were plotted was obtained, Is defined as a moon relaxation rate (MSR). More specifically, it can be measured by the method described in the following examples.

In order to obtain a moonic relaxation rate of 0.45 or more, it is preferable to control the molecular structure so as to lower the branching degree of the modified conjugated diene polymer. For example, when the weight-average molecular weight of the modified conjugated diene polymer is 20 x 10 ⁴ or more and the branching index is 3 or less, it tends to be 0.45 or more. The branching can be controlled by, for example, the number of functional groups of the modifying agent, the amount of the modifying agent added, or the progress of the metallization.

The modified conjugated diene polymer of the present embodiment has a modification ratio of 75 mass% or more from the viewpoint of breaking strength at a high temperature.

The modifying rate means the ratio of the modifying component containing the functional group to the total amount of the conjugated diene polymer.

The functional group contained in the modifying component is not particularly limited, and a functional group that interacts with the surface of the filler in the rubber material is preferable. For example, a functional group containing an element such as nitrogen, oxygen, phosphorus, or tin in a molecule may be mentioned. These elements may contain only one species or two or more species.

The modification ratio can be measured by chromatography capable of separating the modified and non-modified components containing the functional group.

As a method using this chromatography, there can be mentioned a method of using a gel permeation chromatography column in which a polar substance such as silica adsorbing a specific functional group is used as a filler, and quantitatively using an internal standard of non-adsorbed components as a comparison . More specifically, the modification ratio can be calculated from the difference between the chromatogram of the sample and the sample solution containing the low-molecular-weight internal standard polystyrene measured by a polystyrene-based gel column and the silica-based column, . More specifically, the modification ratio can be measured by the method described in the examples.

As a conjugated diene polymer for a fuel-efficient tire, a modifier that imparts affinity to silica for the purpose of improving the affinity with silica incorporated in a tire is used, so that a method of measuring the modifying rate by adsorption to a silica column And is suitably used. In the case of a modifier used for other purposes, it is also presumed that it does not exhibit affinity with silica. In this case, a method of measuring the modifying rate depending on the purpose of the modifier can be selected.

The modification ratio of the modified conjugated diene polymer of the present embodiment is preferably 85% by mass or more, and more preferably 90% by mass or more. The modified conjugated diene polymer having a modifying ratio within this range tends to have a good balance of low hysteresis and wet skid resistance when it is made into a vulcanized product.

The modification ratio of the modified conjugated diene polymer is more preferably 95% by mass or less. With this range, it becomes possible to control the dispersion of the silica particles in the silica blend to an appropriate range, and the stiffness at high temperature can be maintained at a high value. The stiffness at high temperature is a value that is an index of the handling performance at high speed operation. When the modifying ratio is 95 mass% or less, the handling performance at high speed operation tends to be excellent.

The method of controlling the modification ratio to 75% by mass or more tends to be controlled by the amount of the modifier added and the method of adjusting the reaction step.

For example, a method of polymerizing an organic lithium compound having at least one nitrogen atom in the molecule described below as a polymerization initiator, a method of copolymerizing a monomer having at least one nitrogen atom in the molecule, a modification agent of a structural formula described later May be used alone or in appropriate combination so as to control the polymerization conditions so that the chain transfer reaction is not excessively promoted.

As a method of controlling the modifying ratio to 95 mass% or less, there are a method of reducing the amount of the modifying agent (adjusting the number of moles of the functional group bonding to the modifying agent to be smaller than the number of moles of the polymer chain) A method of reducing the addition amount of an organic lithium compound having one nitrogen atom (using organolithium having a nitrogen atom and organolithium having no nitrogen atom as a polymerization initiator) can be exemplified. The modifying ratio at the termination end can be adjusted by adjusting the amount of the modifying agent and adjusting the modifying ratio at the starting end by the amount of the organolithium having the nitrogen atom in the polymerization initiator. The amount of the organolithium having a nitrogen atom in the polymerization initiator and the amount of the organolithium having a nitrogen atom in the polymerization initiator is preferably not more than 5 mass% It needs to be adjusted.

The modified conjugated diene polymer of the present embodiment has a weight average molecular weight of 20 x 10 ⁴ or more and 300 x 10 ⁴ or less.

When the weight average molecular weight is 20 x 10 < ⁴ > or more, the fracture characteristics at a high temperature when made into a vulcanized product tends to increase.

When the weight average molecular weight is 300 x 10 < ⁴ > or less, the Mooney viscosity of the vulcanized product is lowered and the workability tends to be excellent.

The weight average molecular weight of the modified conjugated diene polymer is preferably 50 x 10 ⁴ or more, and more preferably 60 x 10 ⁴ or more. The weight average molecular weight is preferably 200 x 10 ⁴ or less, and more preferably 100 x 10 ⁴ or less.

The weight average molecular weight of the modified conjugated diene polymer and the conjugated diene polymer before modification as described below can be measured based on a calibration curve obtained by using a GPC measuring device and measuring the chromatogram using an RI detector and using standard polystyrene have. Specifically, it can be measured by the method described in the following Examples.

The weight average molecular weight of the modified conjugated diene polymer can be controlled by the molecular weight of the conjugated diene polymer chain controlled by the ratio of the amount of the polymerization initiator used and the amount of the monomer used, the kind of the modifier, and the amount used.

The modified conjugated diene polymer of the present embodiment has a molecular weight distribution (Mw / Mn) of 1.5 or more and 3.5 or less from the viewpoint of the fracture property and workability at high temperature when the material is a vulcanized product.

The molecular weight distribution is preferably 1.7 or more and 3.0 or less, more preferably 1.8 or more and 2.5 or less.

The molecular weight distribution can be controlled within the above-mentioned range by adjusting the molecular weight of the conjugated diene-based polymer chain controlled by the ratio of the amount of the polymerization initiator used and the amount of the monomer used, the kind of the modifier, and the amount used or the polymerization temperature.

The modified conjugated diene polymer of the present embodiment preferably has a nitrogen atom content of 25 mass ppm or more based on the total amount of the modified conjugated diene polymer.

The content of nitrogen atoms (hereinafter also referred to as "nitrogen content") is the total nitrogen atom of the nitrogen-containing functional groups of the modified conjugated diene-based polymer, such as nitrogen-containing functional groups in the starting terminal, main chain and terminal terminal.

The nitrogen content of the modified conjugated diene polymer is preferably 25 mass ppm or more, more preferably 40 mass ppm or more, further preferably 60 mass ppm or more, relative to the total amount of the modified conjugated diene polymer.

When the nitrogen content is in this range, a balance between low hysteresis and wet skid resistance tends to be excellent when the vulcanized product is used. Further, from the viewpoints of workability in the case of using a vulcanized product and dispersibility of the filler, it is preferably 250 mass ppm or less, more preferably 150 mass ppm or less, and further preferably 100 mass ppm or less.

The content of nitrogen atoms can be measured from the oxidation combustion-chemiluminescence method (JIS-2609: crude oil and crude oil product-nitrogen content test method). More specifically, the content of the nitrogen atom can be measured by the method described in the following Examples.

As a method for controlling the nitrogen content of the modified conjugated diene polymer to 25 mass ppm or more, a method of adjusting the addition amount and the reaction of the modifying agent can be mentioned. For example, as a polymerization initiator, there is a method in which at least one nitrogen atom A method of polymerization using an organolithium compound and a method of copolymerizing a monomer having at least one nitrogen atom in a molecule to a conjugated diene polymer having a nitrogen atom to react the modifier having at least one nitrogen atom in the molecule .

In the modified conjugated diene polymer of the present embodiment, the monomer constituting the polymer chain is composed of a conjugated diene compound or a conjugated diene compound and other monomer copolymerizable with the conjugated diene compound.

As the conjugated diene compound, a conjugated diene having 4 to 12 carbon atoms is preferable, and examples thereof include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl- Pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene and 1,3-heptadiene.

Of these, 1,3-butadiene and isoprene are preferred from the viewpoint of industrial availability.

These may be used alone or in combination of two or more.

As the other monomer copolymerizable with the conjugated diene compound, for example, a vinyl aromatic compound is preferable, and styrene is more preferable.

≪ Degenerative residue &

When the modified conjugated diene polymer of the present embodiment has a modifier residue, the modifier residue is a structural unit of the modified conjugated diene polymer to be bonded to the conjugated diene polymer chain, and examples thereof include a conjugated diene polymer and a modifier Which is a structural unit derived from a modifier.

≪ Conjugated diene-based polymer chain having nitrogen atom >

The modified conjugated diene polymer of the present embodiment preferably has a nitrogen atom in at least one of the conjugated diene polymer chains. The structure having a nitrogen atom in the conjugated diene polymer chain includes, for example, a conjugated diene polymer chain having a functional group containing a nitrogen atom at any position. The functional group may be located at the terminal, .

The conjugated diene-based polymer chain having a nitrogen atom can be obtained by, for example, a method of polymerizing a polymerization initiator by using an organic lithium compound having at least one nitrogen atom in a molecule described later, a method of polymerizing a monomer having at least one nitrogen atom Followed by copolymerization.

≪ Modifier residue having silicon atom >

The modified conjugated diene polymer of the present embodiment preferably has a silicon atom in the modifier residue. The modifier residue is, for example, a structural unit derived from a modifier having a silicon atom in a modifier described later.

<Vinyl bond amount>

In the modified conjugated diene polymer of the present embodiment, the vinyl bond amount in the conjugated diene bonding unit is preferably 30 mol% or more from the viewpoint of excellent compatibility with the natural rubber.

The vinyl bond amount is preferably 32 mol% or more and 45 mol% or less, more preferably 35 mol% or more and 40 mol% or less.

The amount of vinyl bond in the conjugated diene bonding unit can be measured by the method described in the following Examples.

The vinyl bonding amount can be controlled as described above by adding a polar compound or adjusting the polymerization temperature.

The modified conjugated diene polymer of the present embodiment is preferably a modified conjugated diene polymer represented by the following general formula (A) or (B). Thus, the balance between low hysteresis and wet skid resistance when vulcanized is excellent is excellent.

In the general formula (A), R ²¹ to R ²⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ each independently represent an alkylene group having 1 to 20 carbon atoms R ²⁷ represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

a, b, c, and d are each independently an integer of 1 or 2, and b and d are 0 or 1, provided that (a + b) and (c + d) 1 &lt; / RTI &gt;

(Polym) represents a conjugated diene compound or a conjugated diene polymer obtained by polymerizing or copolymerizing a conjugated diene compound and an aromatic vinyl compound, wherein at least one terminal thereof is represented by the following general formulas (1) to (4) Functional group.

When there are a plurality of R ²¹ and R ²³ , and a plurality of (Polym) present are independent from each other and may be the same or different.

The modified conjugated diene polymer of the present embodiment may have a molded polymer structure. As the modified polymer structure, for example, in the modified conjugated diene polymer represented by the formula (A), the Si atom bonded to R ²⁵ is taken as a branch point, and the branching point thereof is a linear molecular chain ²⁵ , (OR ²¹ ) _3-ab , R ²² _b and (Polym) _a .

In the general formula (B), R ²⁸ to R ³³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁴ to R ³⁶ each independently represent an alkylene group having 1 to 20 carbon atoms Lt; / RTI &gt;

a, b, c, d, e and f each independently represent a, c and e, provided that (a + b), (c + d) and (e + f) B, d, and f each independently represent an integer of 0 or 1;

(Polym) represents a conjugated diene compound or a conjugated diene polymer obtained by polymerizing or copolymerizing a conjugated diene compound and an aromatic vinyl compound, and at least one terminal thereof is represented by any one of the following general formulas (1) to (4) Represents a functional group to be displayed.

When there are a plurality of R ²⁸ , R ^30, and R ³² , and a plurality of (Polym) present are independent from each other, and they may be the same or different.

The modified conjugated diene polymer of the present embodiment may have a molded polymer structure. As the molded polymer structure, for example, in the modified conjugated diene polymer represented by the general formula (B), the Si atom bonded to R ³⁴ is a branch point, and the branch point thereof is R ³⁴ , (OR ²⁸ ) _3-ab , R ²⁹ _b and (Polym) _a .

In the general formula (1), R ₁₀ and R ₁₁ each independently represent an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 3 to 14 carbon atoms, an aralkyl group having from 6 to 20 carbon atoms, One species.

R ₁₀ and R ₁₁ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure do. The protecting group is also an alkyl-substituted silyl group.

In the general formula (2), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, One species.

R ₁₂ and R ₁₃ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure do.

The protecting group is also an alkyl-substituted silyl group.

R ₁₄ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer chain having 1 to 20 carbon atoms.

In the general formula (3), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 20 carbon atoms, One species.

R ₁₅ and R ₁₆ may combine with each other to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R _{16 each} represent an alkyl group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof. The protecting group is also an alkyl-substituted silyl group.

In the general formula (4), R ₁₇ represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure.

R ₁₈ represents an alkyl group having 1 to 12 carbon atoms or a protecting group, and a part thereof may have a branched structure. The protecting group is also an alkyl-substituted silyl group.

In the general formula (A), R ²¹ to R ²⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

R ²⁵ and R ²⁶ each independently represent an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

R ²⁷ preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom.

Examples of R ²¹ to R ²⁴ include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group, preferably a methyl group and an ethyl group.

Examples of R ²⁵ and R ²⁶ include a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group, and preferably an ethylene group, a propylene group and a butylene group.

Examples of R ²⁷ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group, preferably a hydrogen atom, a methyl group and an ethyl group.

In the general formula (A), the number average molecular weight of (Polym) is not particularly limited, but is preferably 250,000 or more and 1,500,000 or less, and more preferably 350,000 or more and 900,000 or less.

In the general formula (B), R ²⁸ to R ³³ each independently represent an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

R ³⁴ and R ³⁵ each independently represent an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

Examples of R ²⁸ to R ³³ include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, preferably a methyl group and an ethyl group.

Examples of R ³⁴ to R ³⁶ include a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group, and preferably an ethylene group, a propylene group and a butylene group.

In the general formula (B), the number average molecular weight of (Polym) is not particularly limited, but is preferably 250,000 or more and 1,500,000 or less, and more preferably 350,000 or more and 900,000 or less.

In the formula (1), when it is an alkyl group represented by R ₁₀ and R ₁₁ is, R ₁₀ and R ₁₁ preferably represents an alkyl group having 1 to 6 carbon atoms.

When R ₁₀ and R ₁₁ are cycloalkyl groups, it is preferable that R ₁₀ and R ₁₁ represent a cycloalkyl group having 5 to 7 carbon atoms.

When R ₁₀ and R ₁₁ are aralkyl groups, it is preferable that R ₁₀ and R ₁₁ represent an aralkyl group having 6 to 8 carbon atoms.

When R ₁₀ and R ₁₁ are bonded to form a cyclic structure together with the adjacent nitrogen atom, it is preferable that R ₁₀ and R ₁₁ represent an alkyl group having 5 to 7 carbon atoms.

Examples of R ₁₀ and R ₁₁ include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group, preferably a butyl group or an isobutyl group.

When R ₁₀ and R ₁₁ are bonded to form a cyclic structure together with the adjacent nitrogen atom, R ₁₀ and R ₁₁ are not limited to the following examples, and examples thereof include a methylene group, an ethylene group, a propylene group , A butylene group, a pentylene group, and a hexylene group, and preferably a butylene group, a pentylene group or a hexylene group.

In the general formula (2), R ₁₂ and R ₁₃ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms.

Examples of R ₁₂ and R ₁₃ include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, preferably a butyl group or an isobutyl group.

When R ₁₂ and R ₁₃ are bonded to form a cyclic structure together with the adjacent nitrogen atom, R ₁₂ and R ₁₃ are not limited to the following examples. For example, a methylene group, an ethylene group, a propylene group , A butylene group, a pentylene group, and a hexylene group, and preferably a butylene group, a pentylene group or a hexylene group.

In the general formula (2), R ₁₄ preferably represents an alkylene group having 1 to 8 carbon atoms. Examples of the group represented by R ₁₄ include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, and hexylene. Preferred examples of R ₁₄ include an ethylene group, Butylene group.

In the general formula (3), R ₁₅ and R ₁₆ are not limited to the following examples, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group, Ethyl group.

In the general formula (4), R ₁₇ preferably represents an alkyl group having 4 to 6 carbon atoms in total.

It is preferable that R ₁₈ represents an alkyl group having 1 to 4 carbon atoms.

Examples of R ₁₇ include, but are not limited to, a butylene group, a pentylene group, and a hexylene group, and preferably a pentylene group or a hexylene group.

Examples of R ₁₈ include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, preferably a methyl group or an ethyl group.

[Process for producing denatured conjugated diene polymer]

As an example of the method for producing the modified conjugated diene polymer of the present embodiment, an organolithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator, and at least a conjugated diene compound and, if necessary, another monomer are polymerized to form conjugated A polymerization process for obtaining a diene polymer and a modification process for modifying the conjugated diene polymer with a modifier having at least 4 and a tertiary amino group in an alkoxy group bonded to a silyl group in one molecule.

The conjugated diene polymer constituting the modified conjugated diene polymer is a homopolymer of a single conjugated diene compound, a polymer of a different kind of conjugated diene compound, or a copolymer of a conjugated diene compound and an aromatic vinyl compound.

(Polymerization step)

In the polymerization process, as the polymerization initiator, it is preferable to use an organic lithium compound having at least one nitrogen atom in the molecule.

<Polymerization Initiator>

As the polymerization initiator, a polymerization initiator system containing an organolithium compound can be used.

The polymerization initiator system preferably has at least one nitrogen atom in the molecule.

The polymerization initiator system may be prepared by previously preparing an organic lithium compound having at least one nitrogen atom in the molecule in a predetermined reactor or in a reactor for carrying out polymerization or copolymerization to be described later, Before that, a compound having at least one nitrogen atom in the molecule may be reacted with organolithium.

As the compound having at least one nitrogen atom in the molecule, compounds represented by the following general formulas (5) to (7) can be used.

In formula (5), R ₁₀ and R ₁₁ each independently represent an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 3 to 14 carbon atoms, an aralkyl group having from 6 to 20 carbon atoms, and a protecting group One species.

R ₁₀ and R ₁₁ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure do.

The protecting group is also an alkyl-substituted silyl group.

In the general formula (6), R ₁₂ and R ₁₃ each independently represent an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 3 to 14 carbon atoms, an aralkyl group having from 6 to 20 carbon atoms, One species.

R ₁₂ and R ₁₃ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure do.

The protecting group is also an alkyl-substituted silyl group.

R ₁₄ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer chain having 1 to 20 carbon atoms.

X represents a Cl atom, a Br atom, an I atom or a hydrogen atom.

In the general formula (7), R ₁₅ and R ₁₆ each independently represent an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 3 to 14 carbon atoms, an aryl group having from 6 to 20 carbon atoms, Species.

R ₁₅ and R ₁₆ may combine with each other to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R _{16 each} represent an alkyl group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof.

The protecting group is also an alkyl-substituted silyl group.

Examples of R ₁₀ and R ₁₁ in the general formula (5) include, but are not limited to, methyl, ethyl, propyl, butyl, octyl, cyclopropyl, cyclohexyl, 3- Phenyl-1-propyl group, isobutyl group, decyl group, heptyl group and phenyl group.

Examples of the compound represented by the general formula (5) include, but are not limited to, dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, 2-ethylhexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, methylphenethylamine and the like.

The compound represented by the general formula (5) is not limited to these, and, when the above conditions are met, includes the analogues thereof.

The compound represented by the general formula (5) can be used for the purpose of reducing the hysteresis loss of the modified conjugated diene-based polymer composition of the present embodiment described below, reducing the unpleasant odor of the modified conjugated diene polymer of the present embodiment, From the viewpoint of reaction control, dibutylamine and dihexylamine are preferable, and dibutylamine is more preferable.

R ₁₀ and R ₁₁ are bonded to form a cyclic structure together with the adjacent nitrogen atom, examples of the compound represented by the general formula (5) include piperidine, hexamethyleneimine, azacyclooctane, 3,3-trimethyl-6-azabicyclo [3.2.1] octane, and 1,2,3,6-tetrahydropyridine.

The compound represented by the general formula (5) is not limited to these, and, when the above conditions are met, includes the analogues thereof.

The compound represented by the general formula (5) can be used for the purpose of reducing the hysteresis loss of the modified conjugated diene-based polymer composition of the present embodiment described below, reducing the unpleasant odor of the modified conjugated diene polymer of the present embodiment, From the viewpoint of the reaction control, preferred are piperidine, hexamethyleneimine, azacyclooctane and 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, more preferably piperidine, hexamethylene Imine, more preferably piperidine.

In the general formula (6), R ₁₄ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer chain having 1 to 20 carbon atoms.

Examples of the compound represented by the general formula (6) include, but are not limited to, 3-chloro-dimethylpropane-1-amine, 3-chloro- diethylpropane- Chloro-diheptylpropane-1-amine, 3-chloro-dihexylpropan-1 -amine, 3-chloropropyl-ethylhexane- Chloro-ethyl propane-1-amine, 3-chloro-ethyl propane-1-amine, 3-chloro-ethyl propane- 1-amine, 3-chloro-ethyl propane-1-amine, 3-chloro-ethylphenethylpropan- - (3-chloropropyl) hexamethyleneimine, 1- (3-chloropropyl) azacyclooctane, 6- (3-chloropropyl) -1,3,3-trimethyl-6-azabicyclo [3.2.1] , 1- (3-chloropropyl) -1,2,3,6-tetrahydropyridine, 1- (3-bromopropyl) hexamethylene 1- (3-chloropentyl) hexamethyleneimine, 1- (3-chloropentyl) hexamethyleneimine, 1- , 1- (3-chlorodecyl) hexamethyleneimine.

The compound represented by the general formula (6) is not limited to these examples and, when the above conditions are satisfied, includes the analogues thereof.

The compound represented by the general formula (6) is preferably selected from the group consisting of 3-chloro-dibutylpropane-1-amine, 1- (3-chloropropyl) hexamethylene Imine is preferred, and more preferred is 1- (3-chloropropyl) hexamethyleneimine.

In the general formula (6), when R ₁₄ represents a conjugated diene-based polymer chain having any one of the repeating units (8) to (10), X represents a hydrogen atom.

When X represents a hydrogen atom, the compound represented by the general formula (6) is not limited to the following examples, and examples thereof include N, N-dimethyl-2-butenyl- Butenyl-1-amine, N, N-diphenyl-2-butenyl-1-amine, N, N-diheptyl- Butenyl-1-amine, N, N-dihexyl-2-butenyl-1 -amine, N, Propyl-2-butenyl-1-amine, N, N-dimethylacetyl- N-methylphenethyl-2-butenyl-1-amine, N, N-dimethyl- 2-methyl-2-butenyl-1-amine, N, N-diethyl- -Amine, N, N-dipropyl-2-methyl-2-butenyl-1-amine, N, N-diheptyl- Methyl-2-butenyl-1-amine, N, N-dimethyl- Butenyl-1-amine, N, N-dibutyl-3-methyl- Methyl-2-butenyl-1-amine, 1- (2-butenyl) piperidine, 1- (2-butenyl) hexamethyleneimine, 1- (2-butenyl) azacyclooctane, 6- (2-butenyl) 1,3,3-trimethyl-6-azabicyclo [3.2.1] - (2-butenyl) -1,2,3,6-tetrahydropyridine, (2-methyl-2-butenyl) hexamethyleneimine and have.

The compound represented by the general formula (6) is not limited to these examples and, when the above conditions are satisfied, includes the analogues thereof.

From the viewpoint of reducing the hysteresis loss of the modified conjugated diene-based polymer composition of the present embodiment described below, the compound represented by the general formula (2-butenyl) hexamethyleneimine, more preferably 1- (2-butenyl) piperidine and 1- (2-butenyl) hexamethyleneimine, Phenyl) piperidine. &Lt; / RTI &gt;

In the polymerization initiator, the compound represented by the general formula (7) is not limited to the following compounds, and examples thereof include N, N-dimethyl-o-toluidine, N, Dimethyl-p-toluidine, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-dibutyl-o-toluidine, N, N-dibutyl-m-toluidine, N, N-dipropyl- pyrrolidinotoluene, p-pyrrolidinotoluene, N, N, N ', N'-tetramethyltoluenediamine, N, N'-tetramethyltoluenediamine, , N, N ', N'-tetraethyltolylenediamine, N, N, N', N'-tetrapropyltoluenediamine, N, N-dimethylcyclohexylamine, N, (N, N-dimethylamino) toluylphenylmethylamine, N, N-dimethylmethylamine, N, Methylnaphthalene, 1- (N, N-dimethylamino) -2-methylanthracene.

The compound represented by the general formula (7) is not limited to these examples and, if the above conditions are satisfied, includes the analogues thereof.

The compound represented by the general formula (7) is preferably N, N-dimethyl-o-toluidine from the viewpoint of reducing the hysteresis loss of the modified conjugated diene-based polymer composition described later.

The organic lithium compound used as the polymerization initiator is not limited to the following examples, and examples thereof include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium and iso-propyllithium.

The organolithium compound used as the polymerization initiator is preferably one capable of being used as a polymerization initiator for anion polymerization and having at least one nitrogen atom in the molecule from the viewpoints of improving the modification ratio and improving the fuel economy saving performance, 11) to (14).

In the general formula (11), R ₁₀ and R ₁₁ each independently represent an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 3 to 14 carbon atoms, an aralkyl group having from 6 to 20 carbon atoms, Species.

R ₁₀ and R ₁₁ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₀ and R ₁₁ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure do.

The protecting group is also an alkyl-substituted silyl group.

In the general formula (12), R ₁₂ and R ₁₃ are each independently at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, Species.

R ₁₂ and R ₁₃ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₂ and R ₁₃ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure do.

The protecting group is an alkyl substituted silyl group.

R ₁₄ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer having 1 to 20 carbon atoms.

In the general formula (13), R ₁₅ and R ₁₆ each independently represent an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 3 to 14 carbon atoms, an aryl group having from 6 to 20 carbon atoms, Species.

R ₁₅ and R ₁₆ may combine with each other to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ₁₅ and R _{16 each} represent an alkyl group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof.

The protecting group is also an alkyl-substituted silyl group.

In the general formula (14), R ₁₇ represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or branching structure. R ₁₈ represents an alkyl group having 1 to 12 carbon atoms or a protecting group, and a part thereof may have a branched structure.

The protecting group is also an alkyl-substituted silyl group.

Examples of R ₁₀ and R ₁₁ in the general formula (11) include methyl, ethyl, propyl, butyl, octyl, silyltrimethyl, ethylpropylamino, A benzylaminolyl group, and a methylphenethylaminolithiol group.

R ₁₀ and R ₁₁ are not limited thereto and, when the above conditions are met, include the analogues thereof.

From the standpoint of solubility in solvents, the hysteresis loss reduction of the modified conjugated diene polymer composition of the present embodiment described below, and the chain transfer reaction control described later, a dibutylaminol group and a dihexylaminitr group are preferable, Preferably a dibutylamine group.

In the case where R ₁₀ and R ₁₁ are bonded to form a cyclic structure together with the adjacent nitrogen atom in the general formula (11), the organolithium compound represented by the general formula (11) is not limited to the following examples, For example, lithium peroxodisulfate, lithium peroxodisulfate, lithium peroxodisulfate, lithium peroxodisulfate, lithium peroxodisulfate, lithium peroxodisulfate, lithium peroxodisulfate, lithium peroxodisulfate, Dinonyl lithium.

The organolithium compound is not limited to these, and, if the above conditions are met, includes the analogues thereof. From the viewpoints of solubility of the polymerization initiator in a solvent, reduction of the unpleasant odor of the modified conjugated diene polymer of the present embodiment, and suppression of chain transfer reaction, it is preferable to use lithium peroxide such as piperidino lithium, hexamethyleneiminolithium, lithium azacyclooctane , And lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, and piperidino lithium or hexamethyleneiminol lithium is more preferable, and piperidino lithium is more preferable .

In the general formula (12), R ₁₄ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, or a conjugated diene polymer chain having 1 to 20 carbon atoms.

The conjugated diene-based polymer is preferably a conjugated diene-based polymer chain having a repeating unit represented by any one of the following formulas (15) to (17).

In the formula (12), R ₁₄ is a carbon number of 1 to indicate 20 alkylene group of carbon, in view responsiveness and interactivity with the inorganic filler of silica or the like, R ₁₄ is an alkylene group having 2 to 16 And more preferably an alkylene group having 3 to 10 carbon atoms.

When R ₁₄ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent, the organolithium compound represented by formula (12) is not limited to the following examples, and examples thereof include 3- (3- (dipropylamino) -propyl) lithium, (3- (dibutylamino) -propyl) lithium, (3-ethylhexylamino) -propyl) lithium, (3- (dihexylamino) -propyl) lithium, (3- (ethylbutylamino) propyl) lithium, (3- (ethylpropylamino) propyl) lithium, (6- (dibutylamino) -propyl) lithium, (4- (dibutylamino) -butyl) lithium, , And (10- (dibutylamino) -decyl) lithium.

The organolithium compound is not limited to these, and, if the above conditions are met, includes the analogues thereof. (3- (dibutylamino) -propyl) lithium is more preferable from the viewpoints of reactivity and interactivity with inorganic fillers such as carbon, silica and the like.

In the general formula (12), when R ₁₄ represents the conjugated diene polymer chain having the repeating units represented by the above formulas (15) to (17), the organolithium compound represented by the general formula (12) (4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- (dibutylamino) -2- (4- (dihexylamino) -2-butenyl) lithium, (4- (dihexylamino) -2-butenyl) (4- (diethylamino) -2-butenyl) lithium, (4- (di-2-ethylhexylamino) (4- (ethylbutylamino) -2-butenyl) lithium, (4- (ethylbenzylamino) -2-butenyl) ), Lithium (4- (dimethylamino) -2-butenyl) lithium, (4- Methyl-2-butenyl) lithium, (4- (dibutylamino 2-butenyl) lithium, (4- (dipropylamino) -2-methyl-2-butenyl) Butenyl) lithium, (4- (diethylamino) -2-methyl-2-butenyl) Butenyl) lithium, (4- (dipropylamino) -3-methyl-2-butenyl) Lithium), (4- (diheptylamino) -3-methyl-2-butenyl) lithium and (4- (dihexylamino) -3-methyl-2-butenyl) lithium.

The organolithium compound is not limited to these, and, if the above conditions are met, includes the analogues thereof. (4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, or the like) from the viewpoints of reactivity as a polymerization initiator and chain transfer reaction control (4- (dibutylamino) -2-butenyl) lithium is preferable, and more preferable is (4- (dibutylamino) -2-butenyl) lithium.

Examples of the organolithium compound represented by the general formula (12) include, for example, a compound represented by the general formula (12) wherein R ₁₂ and R ₁₃ are bonded to form a cyclic structure together with the adjacent nitrogen atom, (3- (hexamethyleneiminyl) propyl) lithium, (3- (heptamethyleneiminyl) propyl) lithium, (3- (3- (1,2,3,6-tetrahydropyridinyl) propyl) lithium, (2- ( (Hexamethyleneiminyl) ethyl) lithium, (4- (hexamethyleneiminyl) butyl) lithium, (5- (hexamethyleneiminyl) pentyl) (4- (hexamethyleneiminyl) decyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (1,3,3-trimethyl-6-azabicyclo [3.2.1 (3H-imidazolyl) ] Octanyl) -2-butenyl) lithium, (4- (1,2,3,6-tetrahydropyridinyl) -2-butenyl) lithium, (4- (hexamethyleneiminyl) -2-butenyl) lithium, and (4- (hexamethyleneiminyl) -3-methyl-2-butenyl) lithium.

The organolithium compound is not limited to these, and, if the above conditions are met, includes the analogues thereof. (3- (piperidinyl) propyl) lithium, (3- (hexamethyleneiminyl) propyl) lithium (lithium), and the like, from the viewpoints of reactivity and interactivity with inorganic fillers such as silicon, , (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyleneiminyl) -2- (4- (hexamethyleneiminyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, -2-butenyl) lithium, and more preferably (4- (piperidinyl) -2-butenyl) lithium.

Examples of the organolithium compound represented by the general formula (13) include, but are not limited to, N, N-dimethyl-o-toluidino lithium, N, N-dimethyl- N-dimethyl-p-toluidino lithium, N, N-diethyl-o-toluidino lithium, N, N-diethyl- N, N-dipropyl-o-toluidino lithium, N, N-dipropyl-m-toluidino lithium, N, N-dibutyl-m-toluidino lithium, N, N-dibutyl-p-toluidino lithium, o-piperidinotoluenol lithium, p- N, N, N ', N'-tetramethyltolylenediaminolithium, N, N, N', N'-tetramethyltoluenediamine, N, N'-tetramethyldiaminolithium, N, N, N ', N'-tetrapropyltolylenediaminolithium, N, N-dimethylcyclodinolithium, N-dipropyloxy (N, N-dimethylamino) -2 (N, N-dimethylamino) lithium, lithium N, N-dimethylmethidinol lithium, -Methylnaphthalenyl lithium, and 1- (N, N-dimethylamino) -2-methylanthracenol lithium.

The organolithium compound is not limited to these, and, if the above conditions are met, includes the analogues thereof. From the viewpoint of polymerization activity, N, N-dimethyl-o-toluidino lithium is more preferable.

Examples of the organolithium compound represented by the general formula (14) include, but are not limited to, 2- (2-methylpiperidinyl) -1-ethyllithium (for example, Quot;).

The organolithium compound is not limited to these, and, if the above conditions are met, includes the analogues thereof.

Prior to the polymerization step, an organic lithium compound having at least one nitrogen atom in the molecule may be prepared in advance, and any known method can be employed for the production method.

The organolithium compound having at least one nitrogen atom in the molecule represented by the general formula (11) is obtained, for example, by reacting the compound represented by the general formula (5) with an organolithium compound in a hydrocarbon solvent.

As the hydrocarbon solvent, an appropriate solvent such as hexane, cyclohexane, or benzene may be selected. The reaction temperature is preferably 0 deg. C or higher and 80 deg. C or lower, more preferably 5.0 deg. C or more and 70 deg. C or less and more preferably 7.0 deg. C or more and 50 deg. C or less from the viewpoint of productivity.

When the organic lithium compound having at least one nitrogen atom in a molecule, represented by the general formula (12), R ₁₄ represents an alkylene group which may have an aliphatic or aromatic substituent having 1 to 30 carbon atoms, for example, formula ( 6) and an organolithium compound in a hydrocarbon solvent to prepare a lithium amide compound, reacting the same with the dihalogenated alkyl represented by the following general formula (C), and further reacting the organolithium compound .

In the general formula (C), X ¹ and X ² each independently represent an I atom, a Br atom or a Cl atom, and R ^3a represents an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 2 to 16 carbon atoms More preferably an alkylene group having 3 to 10 carbon atoms.

Examples of the compound represented by formula (C) include, but are not limited to, 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1- Bromo-10-chlorodecane, 1-bromo-3-iodopropane, 1-bromo-4-iodobutane, 1- Bromo-10-iododecane, 1-chloro-3-iodopropane, 1-chloro-4-iodobutane, 1- Iodopentane, 1-chloro-6-iodohexane and 1-chloro-10-iododecane.

From the viewpoints of reactivity and safety, the compound represented by the general formula (C) is preferably selected from the group consisting of 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, Bromo-10-chlorodecane, and more preferably 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1- 6-chlorohexane.

The reaction temperature in the production of the lithium amide compound using the compound represented by the general formula (6), the organic lithium compound, and the hydrocarbon solvent is as described above.

The reaction temperature for the reaction of the lithium amide compound with the compound represented by the general formula (C) is preferably from -78 캜 to 70 캜, more preferably from -50 캜 to 50 캜. Thereafter, the reaction temperature at the time of reacting the obtained compound with the organolithium compound is preferably from -78 ° C to 70 ° C, more preferably from -50 ° C to 50 ° C.

The compound represented by the general formula (13) can be synthesized by, for example, reacting a compound represented by the general formula (7) and organic lithium in a hydrocarbon solvent to prepare a lithium amide compound, , And further reacting the organolithium compound.

The reaction temperature in the production of the lithium amide compound using the compound represented by the general formula (7), the organic lithium compound, and the hydrocarbon solvent is as described above.

The reaction temperature when the compound represented by the general formula (C) is reacted with the lithium amide compound is preferably from -78 캜 to 70 캜, more preferably from -50 캜 to 50 캜. Thereafter, the reaction temperature at the time of reacting the obtained compound with the organolithium compound is preferably from -78 ° C to 70 ° C, more preferably from -50 ° C to 50 ° C.

Organic lithium compounds having at least one nitrogen atom in a molecule, represented by the general formula 12, R, if ₁₄ the equation (15) to (17) represents the conjugated diene polymer having a repeating unit represented by any one of , And synthesized into the following steps (I) to (IV).

(I): A compound represented by the general formula (6) and an organic lithium compound are reacted in a hydrocarbon solvent to synthesize a lithium amide compound.

(II); In the hydrocarbon solvent, the obtained lithium amide compound is reacted with butadiene or isoprene.

(III): alcohol is added to deactivate lithium, and the obtained product is subjected to vacuum distillation.

(IV): The product obtained by distillation and the organolithium compound are allowed to react in a hydrocarbon solvent.

The reaction temperature of step (I) for producing lithium amide by using a compound represented by the general formula (6), an organic lithium compound, and a hydrocarbon solvent is as described above. The above-mentioned alcohol can be used in general, but a low molecular weight one is preferable, and for example, methanol, ethanol and isopropanol are preferable, and ethanol is more preferable. The reaction temperature in step (IV) is 0 deg. C or more and 80 deg. C or less, preferably 10 deg. C or more and 70 deg. C or less.

The organolithium compound having at least one nitrogen atom in the molecule represented by the general formula (14) is preferably a compound represented by the general formula (14) when the R ₁₄ represents a conjugated diene polymer having a repeating unit represented by any one of formulas (15) to , And synthesized into the following steps (I) to (IV).

(I): A compound represented by the general formula (7) and an organic lithium compound are reacted in a hydrocarbon solvent to synthesize a lithium amide compound.

(II); In the hydrocarbon solvent, the obtained lithium amide compound is reacted with butadiene or isoprene.

(III): alcohol is added to deactivate lithium, and the obtained product is subjected to vacuum distillation.

(IV): The product obtained by distillation and the organolithium compound are allowed to react in a hydrocarbon solvent.

<Polar compounds>

At the time of producing the above-mentioned organolithium compound, a polar compound may be added in the system. Thereby, there is a tendency to promote the generation and solubilization of the hydrocarbon solvent. Examples of the polar compound include, but are not limited to, tertiary monoamines, tertiary diamines, and linear or cyclic ethers.

Examples of the tertiary monoamine include, but are not limited to, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, N, N-dimethylformamide diisopropyl acetal, and N, N-dimethylformamide dicyclohexyl acetal.

Examples of the tertiary diamine include, but are not limited to, N, N, N ', N'-tetramethyldiaminomethane, N, N, N', N'-tetramethylethylenediamine, N, N, N N, N ', N', N'-tetramethyldiaminobutane, N, N ', N'-tetramethyldiaminopentane, '-Tetramethylhexanediamine, dipiperidinopentane, dipiperidinoethane, and the like.

Examples of the chain ether include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

Examples of cyclic ethers include, but are not limited to, tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, Bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl Oxolanyl) propane.

Of the polar compounds, trimethylamine, triethylamine, which is a tertiary monoamine; N, N, N ', N'-tetramethylethylenediamine, which is a tertiary diamine; Preferred are cyclic ethers such as tetrahydrofuran and 2,2-bis (2-oxolanyl) propane. The polar compounds may be used singly or in combination of two or more.

In the case of adding the polar compound in the production of the above-mentioned organolithium compound, it is preferable to add the polar compound in an amount within the range of 30 mass ppm to 50,000 mass ppm with respect to the solvent used in the production, more preferably 200 mass ppm or more and 20,000 mass ppm or less By mass, more preferably within a range of from 0.1% by mass to 20% by mass.

In order to promote the reaction and solubilization to the solvent, addition of 30 mass ppm or more is preferable, and the degree of freedom in microstructure adjustment in the subsequent polymerization step is ensured, and the solvent after polymerization is recovered and purified It is preferable to add it to 50,000 mass ppm or less.

The conjugated diene polymer prior to modification may be obtained by using a polymerization initiator system comprising an organolithium compound having at least one nitrogen atom in the molecule or a compound having at least one nitrogen atom and an organolithium compound, Or copolymerizing a conjugated diene compound with an aromatic vinyl compound.

In the case where a conjugated diene polymer containing nitrogen atoms is produced as a conjugated diene polymer before modification, an organolithium compound having at least one nitrogen atom in the molecule is previously prepared in a predetermined reactor in the polymerization step, The polymerization reaction may be carried out by feeding the mixture of the conjugated diene compound and the conjugated diene compound or copolymerizing the conjugated diene compound and the aromatic vinyl compound. The compound having at least one nitrogen atom in the molecule and the organolithium compound described above may be introduced into a static mixer or inline Or may be mixed by using a mixer.

When an organic lithium compound having at least one nitrogen atom in the molecule is used as the polymerization initiator system, it may be a single kind or a mixture of two or more kinds.

The conjugated diene polymer prior to modification can be obtained by polymerizing a conjugated diene compound with an aromatic vinyl compound using a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organic lithium compound, By a polymerization process in which the compounds are copolymerized.

The polymerization process may be carried out by any polymerization method such as a batch process or a continuous process. However, from the viewpoint of stably producing a conjugated diene polymer having a high modification ratio, a high molecular weight and a high molecular weight, the polymerization is preferably carried out continuously, It is more preferable to continuously polymerize in two or more connected reactors.

The polymerization process of the organolithium compound may be a continuous process or a batch process. From the viewpoint of production efficiency, a continuous process in which a monomer containing a conjugated diene compound and a polymerization initiator are continuously fed into a polymerization vessel and continuously polymerized is preferred. In the case of the continuous type, the monomers, the solvent and the polymerization initiator used for the polymerization may be separately supplied to the polymerization vessel, or a method using a mixing vessel equipped with a stirrer, a method of continuously mixing the mixture using a static mixer or a line mixer Method may be used.

The polymerization temperature is not particularly limited as long as the anionic polymerization proceeds, the chain transfer reaction is controlled, and the number of the blocks in which the aromatic vinyl compound units are 30 or more in chain is small or absent, but from the viewpoint of productivity, From the viewpoint of controlling the chain transfer reaction and securing a sufficient amount of the modifier to the active terminal after completion of polymerization, it is more preferably 80 ° C or lower, the number of blocks in which the aromatic vinyl units are 30 or more in chain More preferably 50 ° C or more and 78 ° C or less, and still more preferably 60 ° C or more and 75 ° C or less.

In the polymerization process, from the viewpoint of the chain transfer reaction control described above, the content of the conjugated dienic compound, the aromatic vinyl compound, and the aromatic vinyl compound in the total mass of the solvent (the &quot; monomer Concentration ") is preferably at most 16 mass%, more preferably at most 15 mass%, even more preferably at most 14 mass%. The lower limit of the solid content is not particularly limited, but is preferably 12.5 mass% or more.

<Conjugated Diene Polymer>

The conjugated diene polymer before modification of the modified conjugated diene polymer of the present embodiment may be obtained by polymerizing at least a conjugated diene compound in a hydrocarbon solvent and copolymerizing the conjugated diene compound and an aromatic vinyl compound.

The conjugated diene polymer is preferably obtained by an anion polymerization reaction using a continuous polymerization method using an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator. In particular, the conjugated diene polymer is more preferably a polymer having an active terminal obtained by a growth reaction by living anionic polymerization. Thereby, the modified conjugated diene polymer having a high modification ratio can be obtained.

<Conjugated diene compound>

The conjugated diene compound is not limited as long as it is a polymerizable monomer, and examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, , 3-pentadiene, 1,3-heptadiene, and 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are preferred from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

&Lt; Aromatic vinyl compound >

The aromatic vinyl compound is not limited as long as it is a monomer copolymerizable with the conjugated diene compound, and examples thereof include styrene, p-methylstyrene,? -Methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene and diphenylethylene have. Of these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

<Solvent>

The polymerization process is preferably carried out in a solvent. Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specific examples of the hydrocarbon solvent include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, and xylene, and hydrocarbons including mixtures thereof.

The amount of bonded conjugated diene in the conjugated diene polymer before modification of the modified conjugated diene polymer of this embodiment is not particularly limited, but is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 80% .

The amount of the conjugated aromatic vinyl in the conjugated diene polymer before modification of the modified conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 30% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 40% desirable. When the amount of bonded conjugated diene and the amount of bonded aromatic vinyl are in the above range, a balance of low hysteresis loss and wet skid resistance is better, and a vulcanized product having a satisfactory abrasion resistance and breaking strength tends to be obtained. Here, the amount of the conjugated aromatic vinyl can be measured by ultraviolet light absorption of the phenyl group, and the amount of bonded conjugated diene can be obtained from this. Specifically, measurement can be carried out in accordance with the method described in the following Examples.

In the modified conjugated diene polymer of the present embodiment, the amount of vinyl bond in the conjugated diene bonding unit is not particularly limited, but is preferably 30 mol% or more. When the amount of the vinyl bond is within the above range, there is a tendency that the compatibility of the conjugated diene polymer and the natural rubber tends to be excellent, so that the abrasion resistance tends to be excellent when the composition using these is used as the vulcanized product. Here, when the modified conjugated diene polymer is a copolymer of butadiene and styrene, the amount of vinyl bonds in the butadiene bonding unit (1,2-bond (meth) acrylate bond) is determined by the Hampton method (RR Hampton, Analytical Chemistry, 21, 923 Amount) can be obtained. Specifically, the measurement is carried out by the method described in the following examples.

The conjugated diene polymer may be a random copolymer or a block copolymer. Examples of the random copolymer include, but are not limited to, a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, and a butadiene-isoprene-styrene random copolymer. The composition distribution of each monomer in the copolymer chain is not particularly limited and includes, for example, a completely random copolymer having a statistical random composition and a tapered (gradient) random copolymer having a tapered composition. The bonding mode of the conjugated dienes, that is, the composition such as 1,4-bond or 1,2-bond, may be uniform or may be distributed.

Examples of the block copolymer include, but are not limited to, a 2-type block copolymer composed of two blocks, a 3-type block copolymer composed of 3, and a 4-type block copolymer composed of 4 blocks. For example, a block containing an aromatic vinyl compound such as styrene is denoted by S, a block containing a conjugated diene compound such as butadiene or isoprene, and / or a block containing a copolymer of an aromatic vinyl compound and a conjugated diene compound B, they are represented by SB 2 type block copolymer, SBS 3 type block copolymer, SBSB 4 type block copolymer and the like.

In the above equations, the boundaries of the respective blocks need not be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be uniformly distributed or tapered. Further, a plurality of portions in which the aromatic vinyl compound is uniformly distributed and / or a portion in which the aromatic vinyl compound is distributed may coexist in the block B, respectively. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of the block S and the block B are present in the copolymer, the structures such as the molecular weight and the composition may be the same or different.

In the present embodiment, all or part of the double bonds can be converted into saturated hydrocarbons by further hydrogenating the conjugated diene polymer obtained by the above-described production method in an inert solvent. In this case, heat resistance and weather resistance are improved, and there is a tendency to prevent deterioration of the product when it is processed at a high temperature. As a result, it exerts superior performance in various applications such as automobile use.

The hydrogenation rate (also simply referred to as &quot; hydrogenation rate &quot;) of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected depending on the purpose, and is not particularly limited. When used as the vulcanized rubber, it is preferable that the double bonds of the conjugated diene part partially remain. From this viewpoint, the hydrogenation ratio of the conjugated diene part in the polymer is preferably 3.0% or more and 70% or less, more preferably 5.0% or more and 65% or less, still more preferably 10% or more and 60% or less. The hydrogenation ratio of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, more preferably 30% or less, more preferably 20% Or less. Hydrogenation rate can be obtained by nuclear magnetic resonance (NMR).

The hydrogenation is not particularly limited, and a known method can be used. As a suitable hydrogenation method, there can be mentioned a method of hydrogenating a polymer solution in the presence of a catalyst by blowing gaseous hydrogen. As the catalyst, for example, a heterogeneous catalyst such as a catalyst in which a noble metal is supported on a porous inorganic material; A catalyst obtained by solubilizing a salt of nickel, cobalt or the like and reacting with an organic aluminum or the like, or a catalyst using a metallocene such as titanocene. Among them, a titanocene catalyst is preferable from the viewpoint of selecting a mild hydrogenation condition. Further, the hydrogenation of the aromatic group can be carried out by using a noble metal supported catalyst.

Specific examples of the hydrogenation catalyst include, but are not limited to, the following: (1) a supported heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, A so-called Ziegler-type hydrogenation catalyst using a transition metal salt such as an organic acid salt such as Ni, Co, Fe, Cr or an acetylacetone salt and a reducing agent such as an organic aluminum; (3) And so-called organometallic complexes such as metal compounds. As the hydrogenation catalyst, there can be mentioned, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Hydrogenation catalysts described in JP-A-1-53851, JP-A-2-9041, and JP-A-8-109219. As a preferable hydrogenation catalyst, there can be mentioned a reaction mixture of a titanocene compound and a reducing organometallic compound.

If alenes, acetylenes, or the like is contained as an impurity in the conjugated diene compound, there is a fear that the reaction of denaturation to be described later is inhibited. Therefore, the sum of the concentrations (masses) of these impurities is preferably 200 mass ppm or less, more preferably 100 mass ppm or less, and further preferably 50 mass ppm or less, based on the total amount of the conjugated diene compound. The allenes include, for example, propadiene and 1,2-butadiene. The acetylenes include, for example, ethyl acetylene and vinyl acetylene.

When the microstructure (the amount of each bond in the modified conjugated diene-based copolymer) is within the above range and the glass transition temperature of the copolymer is in the range of -45 캜 to -15 캜, low hysteresis loss and wet skid resistance A more excellent vulcanized product can be obtained.

As to the glass transition temperature, according to ISO 22768: 2006, the DSC curve is recorded while the temperature is elevated in a predetermined temperature range, and the peak point of the DSC differential curve is set as the glass transition temperature. Specifically, the measurement is carried out by the method described in the following examples.

When the conjugated diene polymer before modification of the modified conjugated diene polymer of the present embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound, it is preferable that the number of blocks in which the aromatic vinyl units are 30 or more in chain is small or absent. Specifically, when the copolymer is a butadiene-styrene copolymer, the polymer is decomposed by the Kolthoff method (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946) In the known method for analyzing the amount of insoluble polystyrene in methanol is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, based on the total amount of the polymer, of the block having 30 or more aromatic vinyl units .

(Denaturation step)

The production method of the modified conjugated diene-based polymerization of the present embodiment includes a modification step of modifying the conjugated diene polymer with a modifying agent having at least four and tertiary amino groups in an alkoxy group bonded to a silyl group in one molecule.

<Degenerating agent>

Examples of the modifier include, but are not limited to, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy- (3-triethoxysilylpropyl) -1-aza-2-silacyclo pentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) , 2-dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane tris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine , Tris (3-triethoxysilylpropyl) amine, and tris (3-methyldiethoxysilylpropyl) amine.

From the viewpoint of fuel economy saving performance, the modifier preferably includes a modifier represented by any one of the following general formulas (18) to (20).

In the general formula (18), R ¹ to R ⁴ are, each independently represents an aryl group having 1 to 20 carbon alkyl group or having 6 to 20, R ⁵ represents an alkylene group having 1 to 10, R ⁶ is a carbon atoms M represents an integer of 1 or 2, and n represents an integer of 2 or 3. (m + n) is an integer of 4 or more. When a plurality is present, R ¹ to R ⁴ are each independent, and may be the same or different.

In the general formula (19), R ¹ to R ⁶ independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁷ to R ⁹ each independently represent an alkylene group having 1 to 20 carbon atoms M, n and 1 each independently represent an integer of 1 to 3, and (m + n + 1) represents an integer of 4 or more. When a plurality is present, R ¹ to R ⁶ are each independent, and may be the same or different.

In the formula (20), R ¹ to R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁵ and R ⁶ each independently represent an alkylene group having 1 to 20 carbon atoms M and n each independently represents an integer of 1 to 3, (m + n) represents an integer of 4 or more, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Or a silyl group substituted with a hydrocarbon group. When a plurality is present, R ¹ to R ⁴ are independent of each other, and they may be the same or different.

Examples of the modifier represented by the general formula (18) include, but are not limited to, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) , 2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) Silacyclohexane, 2,2-dimethoxy-1- (3-dimethoxy-1-aza- 2-silacyclo pentane, 2-methoxy, 2-methoxy-1- (3-diethoxyethylsilylpropyl) 2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclo pentane, 2- Silacycloheptane, 2-ethoxy, 2-ethyl-1- (3-methoxymethylsilylpropyl) -Diethoxyethylsilylpropyl) -1-aza-2-silacyclopene It can be a shot.

Among them, it is preferable that m is 2 and n is 3 from the viewpoints of reactivity and interactivity between the functional group of the modifier and an inorganic filler such as silica and workability. Specific examples thereof include 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy- ) -1-aza-2-silacyclopentane is preferred.

The reaction temperature, the reaction time, and the like at the time of reacting the modifier of the general formula (18) with the polymerization active end are not particularly limited, but it is preferable to carry out the reaction at 0 ° C or more and 120 ° C or less for 30 seconds or more.

It is preferable that the total number of moles of the alkoxy groups bonded to the silyl group in the compound of the modifier represented by the general formula (18) is in the range of not less than 0.6 times and not more than 3.0 times the number of moles of the alkali metal compound and / or alkaline earth metal compound added in the polymerization initiator , More preferably 0.8 times or more and 2.5 times or less, and still more preferably 0.8 or more and 2.0 times or less. It is preferable that the obtained modified conjugated diene polymer is 0.6 or more times from the viewpoint of obtaining a sufficient modification ratio and a molecular weight and a branched structure. It is preferable to obtain a branched polymer component by coupling the polymer terminals to each other for improving workability In addition, from the viewpoint of the denaturant cost, it is preferably 3.0 times or less.

Examples of the modifier represented by the general formula (19) include, but are not limited to, tris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine, tris (Trimethoxysilylmethyl) amine, tris (2-trimethoxysilylethyl) amine, tris (4-trimethoxysilylbutyl) amine, tris Amines.

Among these, n, m, and l preferably represent 3 from the viewpoints of reactivity and interactivity between the functional group of the modifier and an inorganic filler such as silica and workability. Specific preferred examples include tris (3-trimethoxysilylpropyl) amine and tris (3-triethoxysilylpropyl) amine.

The reaction temperature, the reaction time, and the like at the time of reacting the modifying agent represented by the general formula (19) with the polymerization active end are not particularly limited, but it is preferable to carry out the reaction at 0 ° C or more and 120 ° C or less for 30 seconds or more.

The total number of moles of the alkoxy group bonded to the silyl group in the compound of the modifier represented by the general formula (19) is preferably in the range of 0.6 times or more and 3.0 times or less the number of moles of lithium constituting the above-mentioned polymerization initiator system, Or more and 2.5 times or less, and more preferably 0.8 times or more and 2.0 times or less. From the viewpoint of obtaining a sufficient modification ratio and a molecular weight and a branch structure in the modified conjugated diene polymer, it is preferable to set the molecular weight to 0.6 or more, and it is preferable to couple the polymer terminals to each other to improve the processability to obtain a branched polymer component In addition, from the viewpoint of the denaturant cost, it is preferably 3.0 times or less.

Examples of the modifier represented by the general formula (20) include, but are not limited to, bis (3- (methylamino) propyl) trimethoxysilane, bis (3- Bis (3- (propylamino) propyl) trimethoxysilane, and bis (3- (butylamino) propyl) trimethoxysilane. Of these, n, m, and l are all preferably 3 from the viewpoints of reactivity and interactivity between the functional group of the modifier and an inorganic filler such as silica and workability. Specific preferred examples include bis (3- (methylamino) propyl) trimethoxysilane and bis (3- (ethylamino) propyl) trimethoxysilane.

The reaction temperature, the reaction time, and the like at the time of reacting the modifying agent represented by the general formula (20) with the polymerization active end are not particularly limited, but it is preferable to carry out the reaction at 0 ° C or more and 120 ° C or less for 30 seconds or more.

From the viewpoint of obtaining a modified conjugated diene polymer having a high modification ratio, a high molecular weight and a high branching degree, and a good balance of fuel economy saving performance, processability and abrasion resistance when vulcanized, And a modifier represented by the general formula (19), and further preferably a modifier represented by the general formula (19), wherein m is 2 and n is 3 in the general formula (18) The modifier in which m, n and l are all 3 is preferable.

It is preferable that the total number of moles of alkoxy groups bonded to the silyl group in the compound of the modifier represented by general formula (20) is in the range of not less than 0.6 times and not more than 4.0 times the number of moles of the alkali metal compound and / or alkaline earth metal compound added in the polymerization initiator More preferably 0.8 times or more and 3.5 times or less, and still more preferably 0.8 times or more and 3.0 times or less.

From the viewpoint of obtaining a sufficient modifying ratio of the obtained modified conjugated diene polymer, it is preferable to set it to 0.6 or more. In addition to the fact that it is preferable to couple the polymer terminals to each other to improve the processability to obtain the branched polymer component, , It is preferable to set 4.0 times or less.

From the viewpoint of improving the modification ratio, in the denaturation step, the content of the conjugated diene compound is preferably from 100 mass ppm to 50,000 mass ppm, more preferably from 200 mass ppm to 10000 mass ppm, based on the total amount of all the monomers and the polymer And more preferably 300 mass ppm or more and 5000 mass ppm or less.

In the method for producing the modified conjugated diene-based polymer of the present embodiment, after the denaturation reaction, a deflocculating agent, neutralizing agent and the like may be added to the copolymer solution if necessary. Examples of the defoaming agent include, but are not limited to, water; And alcohols such as methanol, ethanol and isopropanol. Examples of the neutralizing agent include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and bissartic acid; An aqueous solution of an inorganic acid, and carbon dioxide gas.

The modified conjugated diene polymer of the present embodiment is preferably added with a stabilizer for rubber, from the viewpoint of preventing gel formation after polymerization and from the viewpoint of improving the stability at the time of processing. The stabilizer for rubber is not limited to the following, and known stabilizers can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl- -Hydroxy-3 ', 5'-di-tert-butylphenol) propinate and 2-methyl-4,6-bis [(octylthio) methyl] phenol.

In order to improve the processability of the modified conjugated diene-based polymer of the present embodiment, an extender oil may be added to the modified conjugated diene-based copolymer as needed. The method of adding the extensional oil to the modified conjugated diene polymer is not limited to the following method, but it is preferable that the extensional oil is added to the polymer solution and mixed to form a genetic copolymer solution, which is desolvated. Examples of the extender oils include aromatic oils, naphthenic oils and paraffin oils. Of these, from the viewpoint of environmental safety, and oil-bleed prevention and wet grip properties, an aroma replacement oil having a polycyclic aromatics (PCA) content of 3 mass% or less by the IP346 method is preferable. Aromatic substitution oils include, for example, Treated Distillate Aromatic Extracts (TDAE) and Mild Extraction Solvate (MES) as disclosed in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999) and RAE (Residual Aromatic Extracts). The amount of extender oil to be added is not particularly limited, but is preferably 10 parts by mass or more and 60 parts by mass or less, more preferably 15 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the modified conjugated diene polymer.

(Desolvation process)

As a method for obtaining the modified conjugated diene polymer of the present embodiment from the polymer solution, a known method can be used. Examples of such methods include a method of separating a solvent by, for example, steam stripping or the like, followed by filtration of the polymer, dehydration and drying thereof to obtain a polymer, a method of concentrating in a flushing tank and degreasing with a vent extruder , And a method of directly skimming it with a drum dryer or the like.

[Modified conjugated diene polymer composition]

The modified conjugated diene polymer of the present embodiment is suitably used as a vulcanization product.

The vulcanized product can be produced, for example, by mixing the modified conjugated diene polymer of the present embodiment with an inorganic filler such as a silica-based inorganic filler or carbon black, a rubber-like polymer other than the modified conjugated diene polymer of the present embodiment, A vulcanizing accelerator, a vulcanization assistant, etc. to obtain a modified conjugated diene-based polymer composition, followed by heating and vulcanization.

The modified conjugated diene-based polymer composition of the present embodiment comprises a rubber component and a filler in an amount of 5.0 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the rubber component, , And 10% by mass or more of the modified conjugated diene polymer of the present embodiment.

(Rubber component)

As the rubber component used in the modified conjugated diene polymer composition, a rubber-like polymer other than the modified conjugated diene polymer of the present embodiment can be used in combination with the modified conjugated diene polymer of the present embodiment.

Examples of such rubber-like polymers include, but are not limited to, conjugated diene polymers or hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds or hydrogenated products thereof, conjugated diene-based compounds and vinyl aromatic compounds Block copolymers or hydrogenated products thereof, non-diene polymers, and natural rubber.

Examples of the more specific rubber-like polymer include butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene- Or a hydrogenated product thereof, an acrylonitrile-butadiene rubber or a hydrogenated product thereof.

Examples of the rubber-like polymer of the non-diene polymer include, but are not limited to, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene- Olefin elastomers such as octene rubber; Butadiene rubber, butyl rubber, brominated butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber,?,? - unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, have.

The above-mentioned various rubber-like polymers may be modified rubbers obtained by adding functional groups having polarity such as hydroxyl groups and amino groups. The weight average molecular weight thereof is preferably 2,000 or more and 2,000,000 or less, more preferably 5,000 or more and 1,500,000 or less, from the viewpoint of balance between performance and processing characteristics. The weight average molecular weight can be measured by the same method as the method of measuring the modified conjugated diene polymer described in the examples. A so-called liquid rubber having a low molecular weight may also be used as the rubber-like polymer. These rubber-like polymers may be used alone, or two or more of them may be used in combination.

When the modified conjugated diene polymer of the present embodiment and a modified conjugated diene polymer composition containing the rubber-like polymer described above are used, the compounding ratio (ratio by mass) of the modified conjugated diene polymer is preferably (modified conjugated diene polymer / rubber-like polymer) , More preferably 20/80 or more and 100/0 or less, still more preferably 30/70 or more and 90/10 or less, still more preferably 50/50 or more and 80/20 or less. (Modified conjugated diene polymer / rubber-like polymer) falls within the above range, there is a tendency to obtain a vulcanized product having a better balance of low hysteresis loss and wet skid resistance and further satisfying abrasion resistance and fracture strength.

When the modified conjugated diene polymer of the present embodiment is combined with a natural rubber, it is preferable that the modified conjugated diene polymer contains 10 mass% or more of natural rubber relative to the total amount of the rubber component. Thereby, the effect of improving the wear resistance can be obtained.

The modified conjugated diene-based polymer composition of the present embodiment comprises a rubber component and a filler in an amount of 5.0 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the rubber component.

In particular, it is more preferable that 100 parts by mass of the rubber component containing 20% by mass or more of the above-mentioned modified conjugated diene polymer and 150 parts by mass or more of the silica-based inorganic filler are contained.

By dispersing the silica-based inorganic filler in the modified conjugated diene polymer of the present embodiment, when the vulcanized product is made into a vulcanized product, it has excellent balance of low hysteresis loss and wet skid resistance, has practically sufficient abrasion resistance and fracture strength, There is a tendency that excellent workability in water can be imparted.

It is preferable that the modified conjugated diene-based polymer composition of the present embodiment includes a silica-based inorganic filler even when it is used for vulcanized rubber such as automobile parts such as tire, vibration proof rubber, and shoes.

The silica-based inorganic filler is not particularly limited and known ones can be used, but solid particles containing SiO ₂ or Si ₃ Al as a constituent unit are preferable, and SiO ₂ or Si ₃ Al is a main component of the constituent unit More preferable. Here, the main component means a component contained in the silica-based inorganic filler at 50 mass% or more, preferably 70 mass% or more, and more preferably 80 mass% or more.

Examples of the silica-based inorganic filler include, but are not limited to, inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite and glass fiber. As a commercially available product of silica, for example, Ultrasil 7000GR, a product of Ebonic Degussa, can be mentioned. Further, a silica-based inorganic filler whose surface has been hydrophobized, and a mixture of a silica-based inorganic filler and an inorganic filler other than a silica-based filler are also exemplified. Among these, silica and glass fiber are preferable, and silica is more preferable in view of strength and abrasion resistance. Examples of the silica include dry silica, wet silica, and synthetic silicate silica. Of these, wet silica is more preferable from the viewpoint of the effect of improving the fracture characteristics and the balance of the wet skid resistance. The nitrogen adsorption specific surface area determined by the BET adsorption method of the silica-based inorganic filler is preferably 100 m2 / g or more and 300 m2 / g or less from the viewpoint of obtaining good abrasion resistance and breakage characteristics in the modified conjugated diene-based polymer composition , And more preferably from 170 m2 / g to 250 m2 / g. Further, if necessary, a material having a relatively small specific surface area (for example, a silica-based inorganic filler having a specific surface area of 200 m 2 / g or less) and a material having a relatively large specific surface area (for example, Inorganic filler) can be used in combination. This makes it possible to highly balance wear resistance and fracture properties and low hysteresis loss properties.

As described above, the amount of the silica-based inorganic filler to be incorporated in the modified conjugated diene-based polymer composition is not particularly limited so long as the inorganic filler is sufficiently dispersed and the processability and mechanical strength of the composition are practically sufficient. More preferably not less than 5.0 parts by mass and not more than 100 parts by mass, and even more preferably not less than 20 parts by mass and not more than 100 parts by mass, per 100 parts by mass of the rubber component containing the polymer .

The modified conjugated diene-based polymer composition of the present embodiment may contain carbon black. Examples of the carbon black include, but are not limited to, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF. As a commercially available product, for example, trade name "SIST KH (N339)" available from Tokai Carbon Co., Ltd. can be mentioned. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m 2 / g or more and a dibutyl phthalate (DBP) oil absorption amount of 80 mL / 100 g or less is preferable.

The blending amount of the carbon black is preferably 0.5 parts by mass or more and 100 parts by mass or less, more preferably 3.0 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment And more preferably 5.0 parts by mass or more and 50 parts by mass or less. The amount of the carbon black to be blended is preferably 0.5 parts by mass or more from the viewpoint of exhibiting performance required for applications such as dry grip performance and conductivity, and is preferably 100 parts by mass or less from the viewpoint of dispersibility Do.

The modified conjugated diene-based polymer composition of the present embodiment may contain a metal oxide or a metal hydroxide in addition to the silica-based inorganic filler or carbon black. The metal oxide refers to solid particles having the general formula MxOy (M represents a metal atom, and x and y each represent an integer of 1 to 6) as a main component, and examples thereof include alumina, titanium oxide, magnesium oxide, Zinc oxide may be used. Mixtures of inorganic fillers other than metal oxides and metal oxides may also be used. Examples of the metal hydroxide include, but are not limited to, aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

The modified conjugated diene-based polymer composition of the present embodiment may contain a silane coupling agent. The silane coupling agent has a function of tightening the interaction between the rubber component and the silica-based inorganic filler and has an affinity or a bonding group to each of the rubber component and the silica-based inorganic filler. Generally, A compound having an alkoxysilyl group and a silanol group moiety in one molecule is used. For example, bis- [3- (triethoxysilyl) -propyl] -tetra sulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- Silyl) -ethyl] -tetrasulfide. Commercially available products include, for example, the trade name "Si75" available from Ebonic Degussa.

The blending amount of the silane coupling agent is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and even more preferably 1.0 parts by mass or more and 15 parts by mass or more, with respect to 100 parts by mass of the above- Or less. When the blending amount of the silane coupling agent is within the above range, the effect of the addition by the silane coupling agent tends to be more remarkable.

The modified conjugated diene-based polymer composition of the present embodiment may contain a softening agent for rubber in order to improve the processability. As the softener for rubber, mineral oil, liquid softener or low molecular weight synthetic softener are suitable. A mineral oil based softening agent called a process oil or extender oil which is used to improve the softening, expansion and processability of rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and the number of carbon atoms of the paraffin chain is 50 % Or more is referred to as a paraffin system, a naphthene system in which the number of carbon atoms in the naphthene ring is 30% or more and 45% or less, and an aromatic system in which the number of aromatic carbon atoms exceeds 30% is called an aromatic system. As a commercial product, for example, the trade name "JOMO process NC140" of S-RAE oil, Japan Energy Co., Ltd. is mentioned. As the softener for rubber used together with the modified conjugated diene-aromatic vinyl copolymer of the present embodiment, it is preferable that a suitable aromatic content is apt to be compatible with the copolymer.

The amount of softener for rubber is preferably from 0 to 100 parts by mass, more preferably from 10 to 90 parts by mass, per 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment And more preferably 30 parts by mass or more and 90 parts by mass or less. When the compounding amount of the softening agent for rubber is 100 parts by mass or less based on 100 parts by mass of the rubber component, there is a tendency to suppress the bleeding-out and stickiness of the surface of the composition.

The method of mixing the modified conjugated diene polymer of the present embodiment with additives such as other rubber-like polymers, silica-based inorganic fillers, carbon black and other fillers, silane coupling agents, and softening agents for rubber are not particularly limited. As a method therefor, a melt kneading method using a general mixer such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multiaxial screw extruder, etc., Method. Among them, the melt-kneading method using a roll, Banbury mixer, kneader and extruder is preferable from the viewpoint of productivity and good kneading property. Further, the modified conjugated diene polymer and various compounding agents may be kneaded at one time, or a plurality of mixing methods may be applied.

The modified conjugated diene-based polymer composition may be a vulcanized composition obtained by vulcanizing with a vulcanizing agent. Examples of the vulcanizing agent include, but are not limited to, radical generating agents such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds. Sulfur compounds include sulfur monochloride, sulfur dioxide dichloride, disulfide compounds, and polymeric dihalide compounds. The amount of the vulcanizing agent used is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment . As the vulcanization method, conventionally known methods can be applied, and the vulcanization temperature is preferably 120 占 폚 or higher and 200 占 폚 or lower, more preferably 140 占 폚 or higher and 180 占 폚 or lower.

During the vulcanization, a vulcanization accelerator and a vulcanization auxiliary may be used as needed. As the vulcanization accelerator, conventionally known materials may be used. Examples of the vulcanization accelerator include sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate And the like. Specific examples of the compound include N-cyclohexyl-2-benzothiazyl sulfinamide and diphenyl guanidine. The vulcanization auxiliary agent is not limited to the following, and examples thereof include zincation and stearic acid. The amount of the vulcanization accelerator to be used is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment .

The modified conjugated diene-based polymer composition of the present embodiment may contain other softening agents and fillers other than the above-mentioned ones, as well as "SANNOK N" manufactured by Ouchi Shinko Chemical Co., Ltd. Various additives such as waxes, heat stabilizers, antistatic agents, weathering stabilizers, antioxidants such as N-isopropyl-N'-phenyl-p-phenylenediamine, colorants and lubricants may be used. As other softening agents, known softening agents may be used. Other fillers include, for example, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. As the heat stabilizer, the antistatic agent, the weather stabilizer, the anti-aging agent, the colorant and the lubricant, known materials can be used respectively.

The modified conjugated diene-based polymer composition of the present embodiment can be used in the production of a desired rubber product as a rubber composition by adding a vulcanizing agent, a vulcanization accelerator, various additives, and the like.

The rubber composition obtained by crosslinking the modified conjugated diene polymer composition can be used in tires, vibration proof rubber, and various industrial products.

<Examples>

Hereinafter, the present embodiment will be described in more detail by way of specific examples and comparative examples, but the present embodiment is not limited at all by the following examples and comparative examples unless the gist of the present invention is exceeded.

Various physical properties in Examples and Comparative Examples were measured by the following methods.

((Property 1) amount of bound styrene)

Using a modified conjugated diene polymer as a sample, 100 mg of a sample was dissolved in chloroform as a 100 mL solution, and the solution was dissolved to give a measurement sample.

The amount of bound styrene (% by mass) relative to 100% by mass of the denatured conjugated diene polymer serving as a sample was measured by the absorption amount of the ultraviolet absorption wavelength (around 254 nm) of the styrene with the phenyl group (trade name &quot; UV- 2450 &quot;).

((Microstructure (1,2-vinyl bond amount) of butadiene part of (property 2))

Using the modified conjugated diene polymer as a sample, 50 mg of the sample was dissolved in 10 mL of carbon disulfide to prepare a measurement sample.

Using a solution cell, the infrared spectrum was measured in the range of 600 to 1000 cm ^-1 , and the microstructure of the butadiene part, that is, the 1,2-vinyl bond (Mol%) (trade name &quot; FT-IR230 &quot;, manufactured by Nihon Bunko).

(Mooney Viscosity and Mooney Relaxation Rate of (Physical Properties 3) Polymer)

(ISO289-1) and ISO289-4, using a conjugated diene polymer before modification or a modified conjugated diene polymer as a sample using a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) , The Mooney viscosity and the Mooney relaxation rate were measured.

The measurement temperature was 110 캜.

First, the sample was preheated for 1 minute, and then the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain Mooney viscosity (ML _{(1 + 4)} ). Thereafter, when the denatured conjugated diene polymer was used as a sample, the rotation of the rotor was immediately stopped, and the torque for every 0.1 second for 1.6 to 5 seconds after the stop was recorded in terms of Mooney, and the torque and time The slope of the straight line when plotting the number of plots was obtained, and the absolute value of the straight line was determined as the moon relaxation rate (MSR).

((Property 4) Modification Rate)

The modified conjugated diene polymer was used as a sample and measured by applying the property that a denatured component was adsorbed to a GPC column using silica-based gel as a filler.

The sample solution containing the sample and low molecular weight internal standard polystyrene was subjected to measurement of the adsorption amount on the silica column from the chromatogram measured with a polystyrene gel column and the chromatogram measured with a silica column, Respectively.

Specifically, it is as follows.

Sample preparation: 10 mg of sample and 5 mg of standard polystyrene were dissolved in 20 mL of tetrahydrofuran (THF).

Polystyrene column GPC Measurement conditions: THF was used as an eluent, and 200 μL of a sample was injected into the apparatus and measured.

The column was connected to a guard column: TSKguardcolumn HHR-H, manufactured by Tosoh Corporation, and column: TSKgel SuperMultipore HZ-H, manufactured by Tosoh Corporation.

Column chromatography: Oven temperature: 40 DEG C, THF solution in TEA was measured at a flow rate of 1.0 mL / min using an RI detector (trade name &quot; HLC8020 &quot; available from Tosoh Corporation) to obtain a chromatogram.

Silica-based column GPC Measurement conditions: THF was used as an eluent, and 200 μL of a sample was injected into the apparatus and measured.

The column used was the trade name &quot; Zorbax &quot; The column was measured using an RI detector (trade name &quot; HLC8020 &quot; available from Tosoh Corporation) at a column oven temperature of 40 DEG C and a THF flow rate of 0.5 mL / min to obtain a chromatogram.

Calculation method of the modification ratio: The peak area of the sample was defined as P1, the peak area of the standard polystyrene as P2, the total area of the peak area of the chromatogram using the silica-based column, and the total area of the peak area of the chromatogram using the polystyrene- Was 100, the area of the sample was P3, and the peak area of the standard polystyrene was P4, and the modification ratio (%) was calculated from the following formula.

Transformation ratio (%) = [1- (P2 x P3) / (P1 x P4)] x 100

(Where P1 + P2 = P3 + P4 = 100)

((Physical property 5) weight average molecular weight, number average molecular weight)

The chromatogram was measured using a GPC measuring device in which three columns of a denatured conjugated diene polymer or a conjugated diene polymer before addition of a denaturant were used as a sample and a column made of a polystyrene gel as a filler was connected. Using a standard polystyrene The weight average molecular weight (Mw) and number average molecular weight (Mn) were determined based on the obtained calibration curve.

The eluent used was tetrahydrofuran (THF).

The column was used in connection with three guard columns: product name "TSKguardcolumn HHR-H" manufactured by Tosoh Corporation, and column "TSKgel SuperMultipore HZ-H" manufactured by TOSOH CORPORATION. An RI detector (trade name &quot; HLC8020 &quot; manufactured by Tosoh Corporation) was used under the conditions of an oven temperature of 40 DEG C and a THF flow rate of 1.0 mL / min in TEA. 10 mg of a measurement sample was dissolved in 20 mL of THF to prepare a measurement solution, and 200 μL of the measurement solution was injected into a GPC measuring apparatus.

((Property 6) Glass transition temperature (Tg))

Using a denaturing conjugated diene polymer as a sample, the temperature was changed from -100 ° C to 20 ° C / min under flow of helium at a flow rate of 50 ml / min using a differential scanning calorimeter (trade name "DSC3200S" manufactured by Mac Science Inc.) according to ISO 22768: Min, the DSC curve was recorded, and the inflection point of the DSC differential curve was defined as the glass transition temperature.

((Property 7) Nitrogen atom content (mass ppm))

("TN-2100H" manufactured by Mitsubishi Chemical Industries, Ltd.) in accordance with JIS-2609: crude oil and petroleum product-nitrogen fraction test method and chemiluminescence method using the modified conjugated diene polymer as a sample , The emission intensity at 590 to 2500 nm, which is detected by the oxidation reaction of nitrogen monoxide generated by burning oxidation with oxygen gas after pyrolysis of the sample in the presence of argon gas under the condition of dehydration, is measured , And the nitrogen content was determined from the area value of the light emission intensity.

[Example 1] Modified conjugated diene polymer (Sample 1)

An autoclave having an inner volume of 10 L, a ratio L / D of inner diameter L to diameter D of 4.0, an inlet at the bottom, an outlet at the top, and a stirrer and a jacket for temperature adjustment Two units were connected. In addition, at the outlet of the second-stage reactor, 1,3-butadiene obtained by removing one or more impurities such as moisture previously mixed with one static mixer at a rate of 29.0 g / min, styrene at 18.9 g / min and n-hexane at 180.2 g / Respectively. Immediately before the mixed solution was introduced into the first reactor, n-butyllithium for impurity inactivating treatment was supplied at 0.087 mmol / minute, mixed with a static mixer, and then continuously supplied to the bottom of the first reactor. In addition, 2,2-bis (2-oxolanyl) propane was used as a polar material at a rate of 0.018 g / min, and as a polymerization initiator, piperidino lithium ("1-lithiopiperidine" ) And n-butyllithium (molar ratio of piperidino lithium and n-butyllithium is 0.75: 0.25) at a rate of 0.180 mmol / minute to the bottom of the first reactor, The internal temperature was maintained at 65 占 폚. The polymer solution was continuously withdrawn from the top of the reactor at the first stage and continuously fed to the bottom of the reactor at the second stage to continue the reaction at 70 占 폚 and then fed to the static mixer from the top stage of the second stage. A small amount of the copolymer solution before the addition of the modifier was withdrawn from the outlet of the second reactor and added with 0.2 g of antioxidant (BHT) per 100 g of the polymer. Thereafter, the solvent was removed and the Mooney viscosity at 110 캜 was measured to be 51.3 .

Subsequently, to the copolymer solution continuously flowing in the static mixer was added the modifier 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclo pentane shown in Table 1 AS-1 &quot;) was added at a rate of 0.07 mmol / minute to carry out the modification reaction. An antioxidant (BHT) was continuously added to the polymer solution flowing out of the static mixer so that the amount of the antioxidant (BHT) became 0.2 g per 100 g of the polymer, the denaturation reaction was terminated, and then the solvent was removed to obtain a denatured conjugated diene polymer .

As a result of analyzing the sample 1, the Mooney viscosity at 110 ° C was 118, the amount of bound styrene was 36.9 mass%, the amount of vinyl bond (1,2-bond amount) in the butadiene bonding unit was 39.0 mol%, and the modification ratio was 92.3%. Other physical properties of the sample 1 are also shown in Table 1.

[Example 2] Modified conjugated diene polymer (Sample 2)

Modified conjugated diene polymer (Sample 2) was obtained in the same manner as in Example 1 except that the addition amount of the modifier was changed from 0.070 mmol / min to 0.09 mmol / min.

The physical properties of the samples are shown in Table 1.

[Example 3] Modified conjugated diene polymer (Sample 3)

Modified conjugated diene polymer (sample 3) was obtained in the same manner as in Example 1 except that the addition amount of the modifier was changed from 0.070 mmol / min to 0.12 mmol / min.

The physical properties of the samples are shown in Table 1.

[Example 4] A modified conjugated diene polymer (Sample 4)

A modified conjugated diene polymer (sample 4) was obtained in the same manner as in Example 1 except that the molar ratio of lithium piperidino and n-butyl lithium was changed to 0.90: 0.10.

The physical properties of the samples are shown in Table 1.

[Example 5] Modified conjugated diene polymer (Sample 5)

A modified conjugated diene polymer (Sample 5) was obtained in the same manner as in Example 1 except that the molar ratio of lithium piperidino and n-butyllithium was changed to 0.50: 0.50.

The physical properties of the samples are shown in Table 1.

[Example 6] Modified conjugated diene polymer (Sample 6)

The addition amount of the mixed solution of piperidino lithium and n-butyl lithium (the molar ratio of piperidino lithium and n-butyl lithium was 0.75: 0.25) was changed from 0.180 mmol / min to 0.360 mmol / min, Min was changed from 0.07 mmol / min to 0.14 mmol / min, a modified conjugated diene polymer (sample 6) was obtained in the same manner as in Example 1.

The physical properties of the samples are shown in Table 1.

[Example 7] Modified conjugated diene polymer (Sample 7)

The addition amount of a mixed solution of piperidino lithium and n-butyl lithium (the molar ratio of piperidino lithium and n-butyl lithium was 0.75: 0.25) was changed from 0.180 mmol / min to 0.108 mmol / min, Min from 0.07 mmol / min to 0.042 mmol / min, a denatured conjugated diene polymer (sample 7) was obtained in the same manner as in Example 1.

The physical properties of the samples are shown in Table 1.

[Example 8] Modified conjugated diene polymer (Sample 8)

A modified conjugated diene polymer (sample 8) was obtained in the same manner as in Example 1 except that the molar ratio of lithium piperidino and n-butyl lithium was changed to 0.25: 0.75.

The physical properties of the samples are shown in Table 1.

[Example 9] Modified conjugated diene polymer (Sample 9)

(3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was obtained by reacting 2,2-dimethoxy-1- 2 &quot;), a sample 9 was obtained in the same manner as in Example 1.

The physical properties of the samples are shown in Table 1.

[Example 10] Modified conjugated diene polymer (Sample 10)

A sample 10 was obtained in the same manner as in Example 1 except that the addition amount of 2,2-bis (2-oxolanyl) propane as the polar material was changed from 0.018 g / min to 0.09 g / min.

The physical properties of the samples are shown in Table 1.

[Example 11] A modified conjugated diene polymer (sample 11)

Min, the addition amount of 2,2-bis (2-oxolanyl) propane as a polar material was changed from 0.019 g / min to 0.09 g / min, the addition amount of piperidino lithium was changed from 0.162 g / min to 0.18 g / A modified conjugated diene polymer (sample 11) was obtained in the same manner as in Example 1 except that the addition amount of n-butyllithium was changed from 0.018 g / min to 0 g / min, and the addition amount of the modifying agent was changed from 0.07 mmol to 0.09 mmol .

The physical properties of the samples are shown in Table 1.

[Example 12] Modified conjugated diene polymer (Sample 12)

Except that the addition amount of the piperidino lithium was changed from 0.135 g / min to 0.18 g / min, the addition amount of n-butyl lithium was changed from 0.045 g / min to 0 g / min, and the addition amount of the modifier was changed from 0.07 mmol to 0.09 mmol , And the modified conjugated diene polymer (sample 12) was obtained in the same manner as in Example 1.

The physical properties of the samples are shown in Table 1.

[Example 13] A modified conjugated diene polymer (Sample 13)

A modified conjugated diene polymer (sample 13) was obtained in the same manner as in Example 1 except that the molar ratio of piperidino lithium and n-butyl lithium was changed to 0.25: 0.75 and the addition amount of the modifier was changed from 0.07 mmol to 0.09 mmol .

Table 2 shows the physical properties of the samples.

[Example 14] A modified conjugated diene polymer (sample 14)

Minute, the addition amount of the piperidino lithium was changed from 0.135 g / min to 0.27 g / min, the addition amount of n-butyllithium was changed from 0.045 g / min to 0.09 g / min and the addition amount of the modifier was changed from 0.07 mmol to 0.09 mmol , A denatured conjugated diene polymer (sample 14) was obtained in the same manner as in Example 1.

Table 2 shows the physical properties of the samples.

[Example 15] Modified conjugated diene polymer (Sample 15)

Minute, the addition amount of the piperidino lithium was changed from 0.135 g / min to 0.081 g / min, the addition amount of n-butyl lithium was changed from 0.045 g / min to 0.027 g / min and the addition amount of the modifier was changed from 0.07 mmol to 0.09 mmol In the same manner as in Example 1 except for the above, a modified conjugated diene polymer (Sample 15) was obtained.

Table 2 shows the physical properties of the samples.

[Example 16] A modified conjugated diene polymer (sample 16)

(3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was obtained by reacting 2,2-dimethoxy-1- 2) &quot;), and the modified conjugated diene polymer (Sample 16) was obtained in the same manner as in Example 1 except that the addition amount of the modifier was changed from 0.07 mmol to 0.09 mmol.

Table 2 shows the physical properties of the samples.

[Example 17] A modified conjugated diene polymer (sample 17)

Minute, the addition amount of the piperidino lithium was changed from 0.135 g / min to 0.081 g / min, the addition amount of n-butyl lithium was changed from 0.045 g / min to 0.027 g / min and the addition amount of the modifier was changed from 0.07 mmol to 0.09 mmol In the same manner as in Example 1 except for the above, a modified conjugated diene polymer (Sample 17) was obtained.

Table 2 shows the physical properties of the samples.

[Example 18] A modified conjugated diene polymer (sample 18)

Modified conjugated diene polymer (Sample 17) was obtained in the same manner as in Example 1 except that the amount of the modifier was changed from 0.07 mmol to 0.10 mmol.

Table 2 shows the physical properties of the samples.

[Example 19] A modified conjugated diene polymer (Sample 19)

Modified conjugated diene polymer (Sample 19) was obtained in the same manner as in Example 1 except that the amount of the modifier was changed from 0.07 mmol to 0.080 mmol.

Table 2 shows the physical properties of the samples.

[Example 20] A modified conjugated diene polymer (sample 20)

Modified conjugated diene polymer (Sample 20) was obtained in the same manner as in Example 1 except that the amount of the modifier was changed from 0.07 mmol to 0.85 mmol.

Table 2 shows the physical properties of the samples.

[Comparative Example 1] A modified conjugated diene polymer (sample 21)

Modified conjugated diene polymer (sample 21) was obtained in the same manner as in Example 1 except that the addition amount of the modifier was changed from 0.070 mmol / min to 0.047 mmol / min.

Table 2 shows the physical properties of the samples.

[Comparative Example 2] A modified conjugated diene polymer (sample 22)

The addition amount of the mixed solution of piperidino lithium and n-butyl lithium (the molar ratio of piperidino lithium and n-butyl lithium was 0.75: 0.25) was changed from 0.180 mmol / min to 0.400 mmol / min, Min, to 0.155 mmol / min, a denatured conjugated diene polymer (Sample 22) was obtained in the same manner as in Example 1.

Table 2 shows the physical properties of the samples.

[Comparative Example 3] A modified conjugated diene polymer (Sample 23)

Modified conjugated diene polymer (Sample 23) was obtained in the same manner as in Example 1 except that the addition amount of the modifier was changed from 0.070 mmol / min to 0.021 mmol / min.

Table 2 shows the physical properties of the samples.

[Comparative Example 4] The modified conjugated diene polymer (Sample 24)

The addition amount of a mixed solution of piperidino lithium and n-butyl lithium (molar ratio of piperidino lithium and n-butyl lithium was 0.75: 0.25) was changed from 0.180 mmol / min to 0.040 mmol / min, Min, and 0.016 mmol / min to 0.016 mmol / min, a modified conjugated diene polymer (sample 24) was obtained in the same manner as in Example 1.

Table 2 shows the physical properties of the samples.

[Comparative Example 5] A modified conjugated diene polymer (Sample 25)

A modified conjugated diene polymer (sample 25) was obtained in the same manner as in Example 1 except that the molar ratio of piperidino lithium and n-butyl lithium was changed to 0: 1.

Table 2 shows the physical properties of the samples.

[Examples 21 to 40, Comparative Examples 6 to 10] Rubber compositions

Samples (samples 1 to 25) shown in Tables 1 and 2 were used as raw material rubbers, and rubber compositions containing raw rubber were obtained according to the following combinations.

Raw material rubber (Modified conjugated diene polymer (Samples 1 to 25)): 100.0 parts by mass

Filler 1 (silica (trade name &quot; Ultrasil 7000Gr &quot; manufactured by Ebonic Degussa)): 75.0 parts by mass

Filler 2 (carbon black (trade name: "SIST KH (N339)" available from Tokai Carbon Co., Ltd.): 5.0 parts by weight

Silane coupling agent (trade name &quot; Si75 &quot;, product of Ebonic Degussa): 6.0 parts by mass

Process oil (S-RAE oil (trade name &quot; JOMO process NC140 &quot; manufactured by Japan Energy Co., Ltd.)): 30.0 parts by mass

Wax (trade name &quot; Sanok N &quot; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.): 1.5 parts by mass

Zinc conversion: 2.5 parts by mass

Stearic acid: 2.0 parts by mass

2.0 parts by mass of an antioxidant (N-isopropyl-N'-phenyl-p-phenylenediamine)

Sulfur: 1.8 parts by mass

Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazyl sulfinamide): 1.7 parts by mass

Vulcanization accelerator 2 (diphenylguanidine): 2.0 parts by weight

Total: 229.5 parts by mass

[Example 41] Rubber composition

A rubber composition was obtained in the same manner as in Example 21 except that 80.0 parts by mass of the raw rubber (modified conjugated diene polymer (sample 1)) was used and 20.0 parts by mass of the natural rubber was blended.

[Example 42] Rubber composition

A rubber composition was obtained in the same manner as in Example 21 except that 80.0 parts by mass of the raw rubber (modified conjugated diene polymer (Sample 10)) was used and 20.0 parts by mass of the natural rubber was blended.

[Example 43] Rubber composition

A rubber composition was obtained in the same manner as in Example 21 except that 80.0 parts by mass of the raw rubber (modified conjugated diene polymer (sample 11)) was used and 20.0 parts by mass of the natural rubber was blended.

[Comparative Example 11] Rubber composition

A rubber composition was obtained in the same manner as in Example 21 except that 80.0 parts by mass of the raw rubber (modified conjugated diene polymer (Sample 21)) was used and 20.0 parts by mass of the natural rubber was blended.

The above material was kneaded by the following method to obtain a rubber composition.

(Samples 1 to 25), filler 1 (25 g / l), and filler 1 (25 g / l) were kneaded in the first stage using a sealed kneader (content 0.3 L) equipped with a temperature control device under the conditions of a filling rate of 65% , 2 (silica, carbon black), a silane coupling agent, process oil, wax, zincation, and stearic acid were kneaded. At this time, the temperature of the closed mixer was controlled, and each rubber composition was obtained at a discharge temperature (combination) of 155 to 160 ° C.

Next, as the kneading in the second stage, the compound obtained in the above was cooled to room temperature, then an antioxidant was added, and further kneaded to improve the dispersion of silica. In this case, the discharge temperature (combination) was adjusted to 155 to 160 캜 by temperature control of the mixer.

After cooling, as the kneading of the third stage, sulfur and vulcanization accelerators 1 and 2 were added by an open roll set at 70 DEG C and kneaded.

Thereafter, molding was performed, and vulcanization was carried out by a vulcanization press at 160 DEG C for 20 minutes.

The rubber composition before vulcanization and the rubber composition after vulcanization were evaluated.

Specifically, it was evaluated by the following method. The results are shown in Tables 3 to 5.

((Evaluation 1) combination Mooney viscosity)

After the kneading of the second stage and the kneading of the third stage obtained above were used as samples, preheating was carried out at 130 DEG C for one minute in accordance with JIS K6300-1 using a Mooney viscometer, The viscosity was measured after rotating for 2 minutes in two rotations.

In Table 3, Table 4, Comparative Example 6, and Table 5, Comparative Example 11 was evaluated with an index of 100.

The smaller the value, the better the workability.

((Evaluation 2) Viscoelasticity parameter)

The viscoelasticity parameter was measured in a twist mode using a viscoelasticity tester &quot; ARES &quot; manufactured by TA Instrument Japan.

Each measured value was evaluated by an index of 100 for Comparative Example 6 in Table 3, Table 4, and Comparative Example 11 in Table 5.

A frequency of 10 Hz at 0 캜 and tan delta measured at 1% strain were regarded as wet grip properties. The larger the index, the better the wet grip property.

Further, tan? Measured at 50 占 폚 at a frequency of 10 Hz and a strain of 3% was used as an index of low hysteresis loss. The smaller the index, the lower the hysteresis loss is.

G 'measured at 70 ° C at a frequency of 10 Hz and a strain of 3% was regarded as an index of the handling property in high-speed operation. The larger the index, the better the handling performance during high-speed operation.

((Evaluation 3) High Temperature Tensile Properties)

A tensile test was carried out at a measurement temperature of 100 占 폚 using a No. 3 dumbbell-shaped specimen including a rubber composition sheet according to JIS K6251 "Vulcanized Rubber and Thermoplastic Rubber - Method for Determining Tensile Properties" And the evaluation was made with an index of 100 for Comparative Example 6 in Table 3, Table 4, and 100 for Comparative Example 11 in Table 5. The larger the value, the higher the heat resistance.

((Evaluation 4) Abrasion resistance)

The abrasion loss at a load of 44.4 N and 1000 revolutions was measured in accordance with JIS K6264-2 using an Akron abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). In Table 3, Table 4, Comparative Example 6, 11 was evaluated as an index of 100. The larger the index, the better the abrasion resistance.

((Evaluation 5) roll processability)

Using the compound obtained after the kneading of the first stage obtained above as a sample, it was molded using a 3-inch roll to prepare a test piece. The surface of the test piece after molding was evaluated according to the following criteria.

?: Smooth surface with glossy surface.

X: Shrinkage was observed after the roll, and the surface was rough.

As shown in Table 3, Table 4 and Table 5, the modified conjugated diene-based polymer composition using the samples 1 to 20 of the Examples had a higher temperature of the vulcanized product than the modified conjugated diene-based polymer compositions using the samples 21 to 25 of the Comparative Examples It was confirmed that the tensile properties were excellent. Further, it was confirmed that it has excellent balance of low hysteresis loss and wet skid resistance and wear resistance.

INDUSTRIAL APPLICABILITY The modified conjugated diene polymer according to the present invention is industrially applicable in fields such as tire treads, interior and exterior parts of automobiles, anti-vibration rubber, belts, shoes, foams and various industrial products.

Claims (10)

A moonbeam relaxation rate at 110 DEG C of 0.45 or more,
A modification ratio of not less than 75% by mass,
Has a weight average molecular weight (Mw) of 200,000 or more and 3,000,000 or less,
(Weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.5 or more and 3.5 or less,
Modified conjugated diene polymer. The modified conjugated diene polymer according to claim 1, wherein the content of nitrogen atoms is 25 mass ppm or more based on the total amount of the modified conjugated diene polymer. The modified conjugated diene-based polymer according to claim 1 or 2, which is represented by the following general formula (A) or (B).

(In the general formula (A), R ²¹ to R ²⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ each independently represent an alkyl group having 1 to 20 carbon atoms A, b, c, and d are as defined above for (a + b) and (a + b), and R ²⁷ represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. a and c each represent an integer of 1 or 2, and b and d represent an integer of 0 or 1, and (Polym) represents a conjugated diene-based polymer as long as the (c + d) And at least one terminal thereof is a functional group represented by any one of the following general formulas (1) to (4): R ²¹ and R ^{23 in the} presence of a plurality of residues, and a plurality of residues (Polym) It may be different or it may be different)

(In the general formula (B), each of R ²⁸ to R ³³ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁴ to R ³⁶ each independently represent an alkyl group having 1 to 20 carbon atoms A, b, c, d, e, and f are as long as a, c, and e are as long as each of (a + b), (c + d), and B, d and f each independently represent an integer of 0 or 1. (Polym) represents a conjugated diene-based polymer, and at least one terminal thereof is represented by the following general formula (1) (4). When there are a plurality of R ²⁸ , R ^30, and R ³² , and the plurality of (Polym) present are independent of one another, they may be the same or different.

(In the general formula (1), R ¹⁰ and R ¹¹ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, R ¹⁰ and R ¹¹ may combine to form a cyclic structure together with the adjacent nitrogen atom, and in this case, R ¹⁰ and R ^{11 each} represent an alkyl group having 5 to 12 carbon atoms, and an unsaturated bond or a And the protecting group may be an alkyl-substituted silyl group.

(In the general formula (2), R ¹² and R ¹³ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, One species.
R ¹² and R ¹³ may combine to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ¹² and R ¹³ represent an alkyl group having 5 to 12 carbon atoms, and a part thereof has an unsaturated bond or branching structure being.
The protecting group is an alkyl-substituted silyl group.
R ¹⁴ represents an alkylene group having 1 to 30 carbon atoms which may have an aliphatic or aromatic substituent or a conjugated diene polymer chain having 1 to 20 carbon atoms)

(In the general formula (3), R ¹⁵ and R ¹⁶ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 20 carbon atoms, One species.
R ¹⁵ and R ¹⁶ may combine with each other to form a cyclic structure together with the adjacent nitrogen atom. In this case, R ¹⁵ and R ¹⁶ represent an alkyl group having 5 to 12 carbon atoms, and may have a branched structure in a part thereof. Also, the protecting group is an alkyl-substituted silyl group)

(In the general formula (4), R ¹⁷ represents a hydrocarbon group having 2 to 10 carbon atoms and may have an unsaturated bond or branch structure in a part thereof. R ¹⁸ represents an alkyl group having 1 to 12 carbon atoms or a protecting group, And the protecting group may be an alkyl-substituted silyl group. 3. The modified conjugated diene-based polymer according to claim 1 or 2, wherein the moonic relaxation rate at 110 DEG C is less than 0.60. The modified conjugated diene-based polymer according to claim 1 or 2, wherein the moonic relaxation rate at 110 ° C is 0.60 or more and 0.80 or less. The modified conjugated diene-based polymer according to claim 1 or 2, wherein the modification ratio is 95 mass% or less. The modified conjugated diene polymer according to claim 1 or 2, wherein the amount of vinyl bonds in the conjugated diene bonding unit is 30 mol% or more. Rubber component,
A filler in an amount of 5.0 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the rubber component,
Wherein the rubber component comprises 10% or more by mass of the modified conjugated diene polymer as defined in any one of claims 1 to 5, based on the total amount of the rubber component,
Modified conjugated diene-based polymer composition. The modified conjugated diene-based polymer composition according to claim 8, wherein the rubber component comprises at least 10 mass% of a natural rubber based on the total amount of the rubber component. A tire comprising the modified conjugated diene-based polymer composition according to claim 8.