RU2779290C1 - Polymer based on conjugate diene, branching agent, method for production of polymer based on conjugate diene, filled polymer based on conjugate diene, rubber composition, and tire - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to polymer based on conjugate diene. Polymer based on conjugate diene has absolute molecular weight measured using determination of light dissipation in gel-penetrating chromatography (hereinafter – GPC) with a viscosity detector, equal to from 100×10⁴ to 5000×10⁴, and has a number of branches (Bn), measured using determination of light dissipation in GPC with a viscosity detector, equal to from 8 to 84.

EFFECT: development of polymer based conjugate diene, which would have excellent capability of processing in case of using it for the production of vulcanized rubber, and which, in the form of vulcanized rubber, would have excellent balance between a property of low hysteresis losses and slipping resistance on a wet road, as well as abrasion resistance, and would have practically sufficient destruction characteristics.

9 cl, 6 tbl, 51 ex

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0001]

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

BACKGROUND OF THE INVENTION

[0002]

At present, the demand for reducing fuel consumption in vehicles is increasing, and improvements are needed in vehicle tire materials, in particular, in the tread of a tire in contact with the ground.

Recently, there has been a need to develop a material with low rolling resistance, namely low hysteresis loss.

In addition, in order to reduce the weight of a tire, it is necessary to reduce the thickness of a portion of the tire tread, and there is also a need for a material having high abrasion resistance.

On the other hand, from the point of view of safety, it is required that the material used for the tire tread be excellent in wet skid resistance and have practically sufficient breaking characteristics.

[0003]

An example of a rubber material meeting the above requirements includes a rubber material containing a rubbery polymer and a reinforcing filler such as carbon black or silica.

When a silica-containing rubber material is used, the balance between low hysteresis loss property and wet skid resistance can be improved. In addition, an attempt has been made to reduce hysteresis loss by improving the dispersibility of silica in the rubber material by introducing a functional group having affinity or reactivity with silica into the molecular end of the rubbery polymer having high mobility, and by further reducing the mobility of the molecular end of the rubbery polymer by bonding to a silica particle.

[0004]

For example, Patent Documents 1-3 propose a modified conjugated diene based polymer composition obtained by reacting an alkoxysilane having an amino group with an active end of a conjugated diene based polymer and silica.

In addition, Patent Document 4 proposes a conjugated diene-based modified polymer obtained by coupling the active end of a polymer and a multifunctional silane compound.

LIST OF PRIOR ART DOCUMENTS

PATENT DOCUMENTS

[0005]

Patent Document 1: Japanese Patent Application Pending No. 2005-290355

Patent Document 2: Japanese Patent Application Pending No. 11-189616

Patent Document 3: Japanese Patent Application Pending No. 2003-171418

Patent Document 4: International Patent Application No. WO07/114203

SUMMARY OF THE INVENTION

PROBLEMS SOLVED BY THE INVENTION

[0006]

However, the disadvantage of silica is that it is less dispersible in the composition than carbon black because it has a hydrophilic surface and therefore has a low affinity for the conjugated diene polymer, while carbon black has a hydrophobic surface. Therefore, the composition containing silica must further contain a silane modifier and the like. to improve the dispersibility of the silica in the composition by creating a bond between the silica and the conjugated diene polymer.

In addition, when a functional group having a high silica reactivity is introduced into the molecular end of the conjugated diene-based polymer, there is a problem that the workability tends to deteriorate, such as kneading becomes difficult because the reaction with silica particle flows during the kneading process, increasing the viscosity of the resulting composition, or when molded into a sheet after kneading, surface roughness easily occurs or the sheet breaks.

In addition, when such a composition is used to make a vulcanizate, in particular to make a vulcanizate containing an inorganic filler such as silica, there is a problem that the balance between low hysteresis loss property and wet skid resistance, and abrasion resistance are insufficient.

[0007]

Therefore, it is an object of the present invention to provide a conjugated diene-based polymer which has excellent processability when used to make a vulcanizate, and which, in the form of a vulcanizate, has an excellent balance between low hysteresis loss property and wet skid resistance, and also abrasion resistance, and would have practically sufficient fracture characteristics.

TROUBLESHOOTING TOOLS

[0008]

The present inventors have made a serious study to solve the above-described problems of the prior art, and as a result found that a conjugated diene-based polymer having an absolute molecular weight falling within a predetermined range and having a number of branches (Bn) falling within a specific range, has an excellent workability when used to obtain a vulcanizate, and, being in the form of a vulcanizate, has an excellent balance between the property of low hysteresis loss and wet slip resistance and abrasion resistance, and has practically sufficient fracture characteristics, and completed the present invention. In particular, the present invention provides the following:

[0009]

[1] A conjugated diene-based polymer having an absolute molecular weight measured by gel permeation chromatography (GPC) light scattering determination with a viscosity detector of 40 x 10 ⁴ or more and 5000 x 10 ⁴ or less, and having the amount branches (Bn) measured by GPC light scattering determination with a viscosity detector equal to 8 or more.

[2] The conjugated diene-based polymer according to [1] above, having a degree of modification of 60 mass% or more.

[3] The conjugated diene-based polymer according to [1] or [2] above, which has a star polymer structure having 3 or more branches, in which

at least one branched star chain contains a moiety derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and

a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group further contains a branched main chain structure.

[4] The conjugated diene-based polymer according to any of the above paragraphs. [1] - [3], in which

the part obtained from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is a monomer unit based on the compound represented by the following formula (1) or (2), and contains a branching point of a polymer chain containing a monomer unit based on the compound, represented by formula (1) or (2), and

at least one end of the conjugated diene polymer is bonded using a binder:

[0010]

[0011]

[0012]

where in the formula (1) R ¹ represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part;

each of R ² and R ³ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part;

each of R ¹ - R ³ if they are present in the plural, is respectively independent;

X ¹ represents an independent halogen atom;

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3;

in the formula (2), each of R ² to R ⁵ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part, and each of R ² - R ⁵ if they are present in the plural, is respectively independent;

X ² and X ³ represent an independent halogen atom;

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3; and

a represents an integer from 0 to 2, b represents an integer from 0 to 3, c represents an integer from 0 to 3, and (a+b+c) is 3.

[0013]

[5] The conjugated diene-based polymer according to [4] above, containing a monomer unit based on the compound represented by formula (1), in which R ¹ is a hydrogen atom and m is 0.

[6] The conjugated diene-based polymer according to [4] above, containing a monomer unit based on the compound represented by formula (2), in which m is 0 and b is 0.

[7] The conjugated diene-based polymer according to [4] above, containing a monomer unit based on the compound represented by formula (1), in which R ¹ is a hydrogen atom, m is 0, and l is 0.

[8] The conjugated diene-based polymer according to [4] above, containing a monomer unit based on the compound represented by formula (2), in which m is 0, l is 0, a is 0, and b is 0.

[9] The conjugated diene-based polymer according to [4] above, containing a monomer unit based on the compound represented by formula (1), in which R ¹ is a hydrogen atom, l is 0, and n is 3.

[10] The branching agent for the conjugated diene-based polymer according to [4] above, wherein the branching agent is a compound represented by the following formula (1) or (2):

[0014]

[0015]

[0016]

where in the formula (1) R ¹ represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part;

each of R ² and R ³ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part;

each of R ¹ - R ³ if they are present in the plural, is respectively independent;

X ¹ represents an independent halogen atom;

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3;

in the formula (2), each of R ² to R ⁵ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part, and each of R ² - R ⁵ if they are present in the plural, is respectively independent;

X ² and X ³ represent an independent halogen atom;

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3; and

a represents an integer from 0 to 2, b represents an integer from 0 to 3, c represents an integer from 0 to 3, and (a+b+c) is 3.

[0017]

[11] The branching agent according to [10] above, which is the compound represented by the formula (1) in which R ¹ is a hydrogen atom and m is 0.

[12] The branching agent according to [10] above, which is the compound represented by the formula (2) in which m is 0 and b is 0.

[13] The branching agent according to [10] above, which is the compound represented by formula (1), in which R ¹ is a hydrogen atom, m is 0, and l is 0.

[14] The branching agent according to [10] above, which is the compound represented by formula (2) in which m is 0, l is 0, and is 0, and b is 0.

[15] The branching agent according to [10] above, which is the compound represented by formula (1), in which R ¹ is a hydrogen atom, l is 0, and n is 3.

[16] A method for producing a conjugated diene-based polymer according to any one of the above paragraphs. [1] - [9] containing:

a polymerization/branching step of at least a conjugated diene compound in the presence of an organolithium compound to obtain a conjugated diene polymer having a branched main chain structure by using a branching agent according to any of the above. [10] - [15]; and

a step of linking the conjugated diene based polymer by using a binder; and/or a step of modifying the conjugated diene based polymer with a modifier having a nitrogen atom containing group.

[17] The method for producing a conjugated diene-based polymer according to [16] above, wherein the modifier contains a compound represented by any of the following general formulas (A) to (C):

[0018]

[0019]

where each of R ¹ - R ⁴ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, R ⁵ represents an alkylene group having 1-10 carbon atoms, R ⁶ represents an alkylene group, having 1-20 carbon atoms,

m represents the integer 1 or 2, n represents the integer 2 or 3, (m+n) is 4 or greater, and each of R ¹ to R ⁴ , if present in the plural, is respectively independent.

[0020]

[0021]

where each of R ¹ - R ⁶ independently represents an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, each of R ⁷ - R ⁹ independently represents an alkylene group having 1-20 carbon atoms,

each of m, n and l independently represents an integer 1-3, (m+n+1) is 4 or more, and each of R ¹ - R ⁶ if present in the plural, respectively, is independent.

[0022]

[0023]

where each of R ¹² - R ¹⁴ independently represents a single bond or an alkylene group having 1-20 carbon atoms, each of R ¹⁵ - R ¹⁸ and R ²⁰ independently represents an alkyl group having 1-20 carbon atoms, each of R ¹⁹ and R ²² independently represents an alkylene group having 1-20 carbon atoms, R ²¹ represents an alkyl group or a trialkylsilyl group having 1-20 carbon atoms,

m represents an integer 1-3, p is 1 or 2,

each of R ¹² - R ²² , m and p, if present in the plural, is respectively independent, and may be the same or different,

i represents an integer from 0 to 6, j represents an integer from 0 to 6, k represents an integer from 0 to 6, (i+j+k) is 4-10, and

A represents a hydrocarbon group having 1-20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorus atom, and has no active hydrogen.

[0024]

[18] The method for producing a conjugated diene-based polymer according to [17] above, wherein formula (C) A represents any of the following general formulas (II) to (V):

[0025]

[0026]

where B ¹ represents a single bond or a hydrocarbon group having 1-20 carbon atoms, and represents an integer 1-10, and B ¹ if present in the plural, respectively, is independent;

[0027]

[0028]

where B ² represents a single bond or hydrocarbon group having 1-20 carbon atoms, B ³ represents an alkyl group having 1-20 carbon atoms, and represents an integer 1-10, and each of B ² and B ³ if present in the plural, is accordingly independent;

[0029]

[0030]

where B ⁴ represents a single bond or a hydrocarbon group having 1-20 carbon atoms, and represents an integer of 1-10, and B ⁴ if present in the plural, respectively, is independent; and

[0031]

[0032]

where B ⁵ represents a single bond or a hydrocarbon group having 1-20 carbon atoms, and represents an integer of 1-10, and B ⁵ if present in the plural, respectively, is independent.

[0033]

[19] A conjugated diene-based filled polymer comprising:

100 m.h. a polymer based on a conjugated diene in accordance with any of the above paragraphs. [19]; and

1-60 m.h. at least one substance selected from the group consisting of a filling oil, a latex and a resin.

[20] A rubber composition comprising:

rubber component; and

5.0 m.h. or more and 150 m.ch. or less filler per 100 m.h. rubber component

in which the rubber component contains, by total weight of the rubber component, 10 wt.% or more of the polymer based on a conjugated diene in accordance with any of the above paragraphs. [1] - [9] or a filled polymer based on a conjugated diene according to [19] above.

[21] A tire containing a rubber composition according to [20] above.

BENEFICIAL EFFECTS OF THE INVENTION

[0034]

According to the present invention, a conjugated diene-based polymer can be obtained which is excellent in workability when used to make a vulcanizate, and which, when in the form of a vulcanizate, can realize an excellent balance between low hysteresis loss property and wet slip resistance. road, has high abrasion resistance and practically sufficient fracture characteristics.

METHOD FOR CARRYING OUT THE INVENTION

[0035]

Next, one embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail.

It should be noted that the following present embodiment is merely an example for describing the present invention, and the present invention is not limited to this description and may be modified in various ways within its scope.

[0036]

[Conjugated diene polymer]

The conjugated diene-based polymer of the present embodiment has an absolute molecular weight measured by gel permeation chromatography (GPC) light scattering determination with a viscosity detector of 40 x 10 ⁴ or more and 5000 x 10 ⁴ or less, and the number of branches ( Bn) obtained by gel permeation chromatography (GPC) light scattering determination with a viscosity detector of 8 or more.

The conjugated diene-based polymer having the above absolute molecular weight and number of branches has an extremely excellent workability when used to make a vulcanizate, and in the form of a vulcanizate, it has an excellent balance between low hysteresis loss property and wet skid resistance, and also abrasion resistance, and has practically sufficient fracture characteristics.

[0037]

The conjugated diene-based polymer of the present embodiment has a modification degree of preferably 60 wt% or more.

The modified conjugated diene based polymer having the above absolute molecular weight, the number of branches and the degree of modification has an extremely excellent workability when it is used to make a vulcanizate, and in the form of a vulcanizate it has an excellent balance between the property of low hysteresis loss and slip resistance on wet road, as well as resistance to abrasion and practically sufficient destruction characteristics.

It should be noted that the term "conjugated diene polymer" in this document also covers the modified conjugated diene polymer obtained after modification, unless expressly stated otherwise.

[0038]

(absolute molecular weight)

In terms of processability, balance between low hysteresis loss property and wet slip resistance, abrasion resistance, and fracture characteristics, the conjugated diene-based polymer of the present embodiment has an absolute molecular weight obtained by gel permeation chromatography light scattering determination ( GPC) with a viscosity detector, 40 x 10 ⁴ or more and 5000 x 10 ⁴ or less.

Typically, a polymer having a branched structure has a smaller molecule compared to a linear chain polymer having the same molecular weight. Therefore, when using the molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC), which is a relative comparison with a standard polystyrene sample to classify the polymer according to molecular size, the molecular weight of the polymer having a branched structure is generally underestimated. .

On the other hand, with respect to the absolute molecular weight measured by the gel permeation chromatography (GPC) light scattering detection with a viscosity detector, the molecular weight (absolute molecular weight) is measured by directly observing the molecular size by the light scattering method, and therefore , compared to the molecular weight in terms of polystyrene obtained using gel permeation chromatography (GPC), is independent of the polymer structure or interaction with the column fill. Therefore, the molecular weight can be accurately measured regardless of the structure of the polymer, such as a branched structure of a polymer based on a conjugated diene.

[0039]

The absolute molecular weight of the conjugated diene polymer of the present embodiment is 40 x 10 ⁴ or more, preferably 50 x 10 ⁴ or more, more preferably 60 x 10 ⁴ or more, even more preferably 80 x 10 ⁴ or more, and most preferably 100 x 10 ⁴ or more.

The absolute molecular weight of the conjugated diene based polymer of the present embodiment is 5000 x 10 ⁴ or less, preferably 4500 x 10 ⁴ or less, more preferably 4000 x 10 ⁴ or less, even more preferably 3500 x 10 ⁴ or less, and most preferably 3000 x 10 ⁴ or less.

When the absolute molecular weight is 40x10410 ⁴ or more, the balance between the low hysteresis loss property and the wet skid resistance, as well as the abrasion resistance in the form of the vulcanizate, is excellent. When the absolute molecular weight is 5000x104 or less, the vulcanizate processability and filler dispersibility are excellent, and practically sufficient fracture characteristics can be obtained.

The absolute molecular weight of the conjugated diene based polymer can be measured by the method described below in the examples.

The absolute molecular weight of the conjugated diene based polymer of the present embodiment can be controlled to fall within the above-described numerical range by adjusting the amount of polymerization initiator added, the amount of branching agent functionality, the amount of branching agent added, the time of adding branching agent, as well as the added amounts binder and modifier.

[0040]

(Number of branches)

From the viewpoints of processability, balance between low hysteresis loss property and wet skid resistance, abrasion resistance, and fracture characteristics, the number of branches (Bn) of the conjugated diene-based polymer of the present embodiment is 8 or more.

The number of branches (Bn) of 8 or more means that the conjugated diene-based polymer of the present embodiment has 8 or more polymer chains as side chains relative to the substantially longest main polymer chain.

The number of branches (Bn) of the conjugated diene based polymer is determined by using the compression factor (g') as measured by gel permeation chromatography (GPC) light scattering determination with a viscosity detector as g' = 6Bn/{(Bn+1) (Bn+2)}.

[0041]

Typically, a polymer having a branched structure has a smaller molecule compared to a linear chain polymer having the same absolute molecular weight.

The contraction factor (g') is a measure of the ratio to the size occupied by a molecule in a linear chain polymer that has the same absolute molecular weight. In other words, as the number of polymer branches increases, the compression factor (g') tends to decrease.

For the compression factor in this embodiment, intrinsic viscosity is used as the molecular size index, and the linear chain polymer satisfies the relationship: intrinsic viscosity [η] = -3.883 M ^0.771 where M represents the absolute molecular weight.

The contraction factor (g'), however, expresses the ratio of molecular size reduction, and does not accurately express the structure of the polymer arms.

Therefore, the number of branches (Bn) of the conjugated diene based polymer is calculated using the value of the compression factor (g') obtained for each absolute molecular weight of the conjugated diene based polymer. The "number of branches (Bn)" thus calculated accurately expresses the number of polymers directly or indirectly linked to the longest main chain structure.

The calculated number of branches (Bn) can serve as an index expressing the branched structure of the conjugated diene based polymer. For example, in a typical 4-arm star polymer (having 4 polymer chains connected to the core), two polymer chains are linked to the longest main chain structure, and therefore the number of branches (Bn) is estimated to be 2.

In a typical 8-arm star polymer, 6 polymer chains are linked to the longest main chain structure, and the number of arms (Bn) is estimated to be 6.

The conjugated diene based polymer of the present embodiment has a number of branches (Bn) of 8 or more, which means that it is a conjugated diene based polymer having at least 10 branches as a star polymer structure.

Here, the "branch" is formed by direct or indirect bonding of one polymer to another polymer. In addition, the "number of branches (Bn)" corresponds to the number of polymers directly or indirectly linked to the longest main chain structure.

When the number of branches (Bn) is 8 or more, the conjugated diene-based polymer of the present embodiment in the form of a vulcanizate has an excellent balance between low hysteresis loss property and wet skid resistance.

In most cases, an increase in absolute molecular weight tends to worsen workability, and when the absolute molecular weight increases in the structure of a linear chain polymer, the vulcanizate obtained from it becomes much more viscous and its workability deteriorates significantly. Therefore, even when a large amount of functional groups are introduced into the polymer to improve the affinity and/or reactivity with the silica added as a filler, the silica cannot be sufficiently dispersed in the polymer during the kneading process. As a result, the function of the introduced functional groups cannot be exhibited, and therefore, the initially expected effect of improving the property of low hysteresis loss and wet skid resistance by introducing the functional groups cannot be exhibited.

On the other hand, since the conjugated diene-based polymer of the present embodiment has a number of branches (Bn) of 8 or more, the increase in viscosity of the vulcanizate obtained therefrom due to the increase in absolute molecular weight is largely suppressed, and therefore, this polymer can be sufficiently mixed with silica, etc. during mixing so that the silica can be dispersed around the conjugated diene based polymer. As a result, the abrasion resistance and fracture characteristics can be improved by increasing the molecular weight of the conjugated diene based polymer, and in addition, the silica can be dispersed around the polymer by sufficiently interfering so as to allow the functional groups to act and/or react, and thus , the polymer can achieve practically sufficient properties of low hysteresis loss and wet skid resistance.

The absolute molecular weight of the conjugated diene based polymer can be measured by the method described below in the examples.

[0042]

The number of branches (Bn) of the conjugated diene polymer of the present embodiment is 8 or more, preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more.

A conjugated diene-based polymer having a number of branches (Bn) in this range tends to be excellent in workability when used to make a vulcanizate.

The upper limit of the number of branches (Bn) is not particularly limited, and may be equal to or greater than the detection limit, and is preferably 84 or less, more preferably 80 or less, even more preferably 64 or less, and most preferably 57 or less.

If the number of branches is 84 or less, the abrasion resistance obtained for the vulcanizate tends to be excellent.

The number of branches of the conjugated diene based polymer can be controlled to be 8 or more according to the combination of the amount of branching agent added and the amount of end modifier added. In particular, the number of branches can be controlled in accordance with the number of functional groups of the branching agent, the amount of the branching agent added, the timing of the addition of the branching agent, and the amount of the modifier added. A more specific description will be given in [Method for producing a polymer based on conjugated diene] described below.

[0043]

(Degree of modification)

From the viewpoints of processability, balance between low hysteresis loss property and wet skid resistance, abrasion resistance, and fracture characteristics, the conjugated diene-based polymer of the present embodiment preferably has a modification degree of 60 wt.% or more based on the total weight of the conjugated diene-based polymers. diene.

As used herein, the term "degree of modification" refers to the weight ratio of a conjugated diene-based polymer having a nitrogen-containing functional group to the total amount of conjugated diene-based polymers.

For example, assuming that the nitrogen-containing modifier reacts with the chain end, the weight ratio of the conjugated diene-based polymer having a nitrogen-containing functional group due to the nitrogen-containing modifier to the total number of conjugated diene-based polymers is expressed as the degree of modification.

On the other hand, also when the polymer is branched by using a nitrogen-containing branching agent, the thus obtained conjugated diene-based polymer has a nitrogen-containing functional group, and such a branched polymer is also taken into account in calculating the degree of modification.

In other words, herein, when the conjugated diene-based polymer is specifically "modified conjugated diene-based polymer", the mass fraction of the sum of the binder polymer obtained using the modifier having a nitrogen-containing functional group and/or the branched polymer obtained with using a branching agent having a nitrogen-containing functional group corresponds to the degree of modification.

The degree of modification is preferably 65 wt% or more, more preferably 70 wt% or more, even more preferably 75 wt% or more, even more preferably 80 wt% or more, and most preferably 82 wt% or more.

If the degree of modification is 60% by mass or more, the resulting polymer tends to have excellent workability as a vulcanizate, as well as excellent abrasion resistance and low hysteresis loss property as a vulcanizate.

[0044]

The degree of modification can be measured using chromatography capable of separating the functional group-containing modified component and the unmodified component.

As a method using chromatography, a method using a gel permeation chromatography column filled with a polar material such as silica adsorbing a specific functional group can be used to perform a quantitative determination using an internal standard of a non-adsorbed component.

More specifically, the degree of modification is obtained by measuring the amount of adsorption on a silica column based on the difference between a chromatogram measured using a polystyrene gel column and a chromatogram measured using a silica column for a sample solution containing a sample and an internal standard. low molecular weight polystyrene. More specifically, the degree of modification is measured by the method described in the examples below.

[0045]

In the conjugated diene-based polymer of the present embodiment, the degree of modification can be controlled by adjusting the addition amount of the modifier and the reaction method, and thus can be maintained at 60 mass% or more.

For example, a method in which polymerization is performed using the following organolithium compound having at least one nitrogen atom in a molecule as a polymerization initiator, a method in which a monomer having at least one nitrogen atom in a molecule is copolymerized, and also a method in which a modifier having the structural formula described below is used and the polymerization conditions can be controlled so that a desired degree of modification is obtained.

[0046]

From the viewpoint of the balance of workability and abrasion resistance, the conjugated diene based polymer of the present embodiment is preferably a conjugated diene based polymer having a star structure having 3 or more branches, in which at least one branch of the star structure contains a portion derived from a monomer a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and a part derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, further comprises a branched main chain structure.

As used herein, the term "polymer star structure" refers to a structure in which a plurality of polymer chains (branches) are linked to a single central branch point.

One central branching point herein contains "a substituent containing an atom derived from a binder" or "a substituent containing a nitrogen atom derived from a modifier".

The term "main branch structure" herein refers to a structure in which a polymer chain forms a branch point in a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and the polymer chain (branch) emerges from this branch point.

[0047]

In the conjugated diene-based polymer of the present embodiment, from the viewpoint of improving the number of Bn branches, the number of main chain branching points constituted by the part obtained from the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is 4 or more, and the branched structure obtained from the polymer star structure formed by the modifier in the reaction step preferably contains 3 or more branches, more preferably 4 or more branches, and even more preferably 8 or more branches.

Although the number of Bn branches is increased both by modification with a binder to obtain a star structure and by introducing a branching agent into the polymer, the contribution to the number of Bn branches becomes larger when the entire polymer chain is branched by using a binder.

In polymer development, the number of Bn branches can be controlled according to the selection of the binder and the selection of the type and amount of the branching agent, and the number of Bn branches can be more easily controlled considering the contribution rate.

[0048]

<Branched Main Circuit Structure>

The branched main chain structure corresponds to the branch points in the portion derived from the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and contains 2 or more branch points, preferably 3 or more branch points, and even more preferably 4 or more branch points.

The branch point forming the main branch structure preferably has at least 2 or more polymer chains, more preferably 3 or more non-main chain polymer chains, and even more preferably 4 or more non-main chain polymer chains.

In particular, in a branched main chain structure containing a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, the peak of the branched main chain structure is found when performing ²⁹ Si-NMR in the range of -45 ppm to -65 ppm, and more strictly in the range of -50 ppm to -60 ppm.

[0049]

<Resin Star Structure>

The conjugated diene based polymer of the present embodiment preferably has a star structure, and the number of branches in the star structure of the polymer is preferably 3 or more, more preferably 4 or more, even more preferably 6 or more, and most preferably 8 or more.

[0050]

In the production method as a conjugated diene polymer of the present embodiment, a conjugated diene polymer having a polymer star structure containing 3 or more branches, in which at least one star structure branch contains a part obtained from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and a portion obtained from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group further contains a branched main chain structure, a "star-shaped polymer structure" can be formed by adjusting the amount of functional groups of the modifier and the amount of modifier added, and The "main chain branching structure" can be controlled by adjusting the amount of functional groups of the branching agent, the amount of branching agent added, and the time of adding the branching agent.

[0051]

In order to obtain a conjugated diene-based polymer having a polymer star structure having 3 or more branches, in which at least one star structure branch contains a part derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and a part , obtained from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group additionally, contains a branched main chain structure, can be used, for example, a method in which polymerization is performed using an organolithium compound as a polymerization initiator, a branching agent to create a specific branch point is added during or after polymerization, and the modification is performed using a modifier to impart a specific branching factor after continued polymerization.

The controls for such polymerization conditions will be described later as a manufacturing method in the examples.

[0052]

(Detailed structure of branched main circuit structure)

The conjugated diene-based polymer of the present embodiment is preferably a conjugated diene-based polymer in which a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is a monomer unit based on the compound represented by the following formula (1) or (2) contains a polymer chain branch point containing a monomer unit based on the compound represented by formula (1) or (2), and has at least one conjugated diene-based polymer end of the present invention bonded by using a binder, and at least one end of the conjugated diene polymer is more preferably modified with a nitrogen containing group.

[0053]

[0054]

[0055]

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part.

Each of R ² and R ³ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part. Each of R ¹ - R ³ if they are present in the plural, is respectively independent.

X ¹ represents an independent halogen atom.

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3.

In the formula (2), each of R ² to R ⁵ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part.

Each of R ² - R ⁵ if they are present in the plural, is respectively independent.

X ² and X ³ represent an independent halogen atom.

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and

(m+n+l) is equal to 3.

a represents an integer from 0 to 2, b represents an integer from 0 to 3, c represents an integer from 0 to 3, and (a+b+c) is 3.

[0056]

The conjugated diene-based polymer of the present embodiment preferably has a monomer unit based on the compound represented by formula (1) in which R ¹ is a hydrogen atom and m is 0.

Thus, the number of branches is improved, and the effect of improving abrasion resistance and workability can be obtained.

[0057]

Alternatively, the conjugated diene based polymer of the present invention is preferably a conjugated diene based polymer having a monomer unit based on the compound represented by formula (2) in which m is 0 and b is 0.

Thus, an effect of improving abrasion resistance and workability can be obtained.

[0058]

As another alternative, the conjugated diene-based polymer of the present embodiment preferably has a monomer unit based on the compound represented by formula (1) in which R ¹ is a hydrogen atom, m is 0, and l is 0.

Thus, the number of branches is improved, and the effect of improving abrasion resistance and workability is obtained.

[0059]

Alternatively, the conjugated diene based polymer of the present embodiment is preferably a conjugated diene based polymer having a monomer unit based on the compound represented by formula (2) in which m is 0, l is 0, and is 0, and b is 0.

Thus, an effect of improving abrasion resistance and workability can be obtained.

[0060]

The conjugated diene based polymer of the present embodiment is more preferably a conjugated diene based polymer having a monomer unit based on the compound represented by formula (1) in which R ¹ is a hydrogen atom, l is 0, and n is 3.

Thus, the degree of modification and the number of branches are improved, and the effect of improving fuel efficiency, abrasion resistance, and workability can be obtained.

[0061]

[Branch Agent]

In the conjugated diene-based polymer of the present embodiment, when constructing the branched main chain structure, the branching agent represented by the following formula (1) or (2) is preferably used as the branching agent.

[0062]

[0063]

[0064]

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part.

Each of R ² and R ³ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part.

Each of R ¹ - R ³ if they are present in the plural, is respectively independent.

X ¹ represents an independent halogen atom.

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and

(m+n+l) is equal to 3.

In the formula (2), each of R ² to R ⁵ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part.

Each of R ² - R ⁵ if they are present in the plural, is respectively independent.

X ² and X ³ represent an independent halogen atom.

m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and

(m+n+l) is equal to 3.

a represents an integer from 0 to 2, b represents an integer from 0 to 3, c represents an integer from 0 to 3, and (a+b+c) is 3.

[0065]

In the present embodiment, from the viewpoints of polymerization continuity and improvement in the number of branches, the branching agent used in constructing the branched structure of the conjugated diene-based polymer backbone is preferably the compound represented by the formula (1) in which R ¹ is a hydrogen atom and m is 0.

[0066]

Alternatively, in the present embodiment, from the viewpoint of improving the number of branches, the branching agent used in constructing the branched structure of the conjugated diene polymer backbone is preferably the compound represented by the formula (2) in which m is 0 and b is 0.

[0067]

In the present embodiment, from the viewpoints of polymerization continuity and improvement of the degree of modification and the number of branches, the branching agent used in constructing the branched structure of the conjugated diene-based polymer backbone is more preferably the compound represented by the formula (1) in which R ¹ is a hydrogen atom , m is 0 and l is 0.

[0068]

In the present embodiment, from the viewpoint of improving the degree of modification and the number of branches, the branching agent used in constructing the branched structure of the conjugated diene polymer backbone is even more preferably the compound represented by the formula (2) in which m is 0, l is 0 , and is equal to 0 and b is equal to 0.

[0069]

In the present embodiment, from the viewpoints of polymerization continuity and improvement of the degree of modification and the number of branches, the branching agent used in constructing the branched structure of the conjugated diene-based polymer backbone is more preferably the compound represented by the formula (1) in which R ¹ is a hydrogen atom , l is 0 and n is 3.

[0070]

Examples of the branching agent represented by formula (1) include, but are not limited to, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, tripoxy(4-vinylphenyl)silane, tributoxy(4-vinylphenyl)silane, triisopropoxy(4-vinylphenyl)silane, trimethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane, tripropoxy(3-vinylphenyl)silane, tributoxy(3-vinylphenyl)silane, triisopropoxy(3-vinylphenyl)silane, trimethoxy( 2-vinylphenyl)silane, triethoxy(2-vinylphenyl)silane, tripropoxy(2-vinylphenyl)silane, tributoxy(2-vinylphenyl)silane, triisopropoxy(2-vinylphenyl)silane, dimethoxymethyl(4-vinylphenyl)silane, diethoxymethyl(4- vinylphenyl)silane, dipropoxymethyl(4-vinylphenyl)silane, dibutoxymethyl(4-vinylphenyl)silane, diisopropoxymethyl(4-vinylphenyl)silane, dimethoxymethyl(3-vinylphenyl)silane, diethoxymethyl(3-vinylphenyl)silane, dipropoxymethyl(3-vinylphenyl) silane, dibutoxymethyl(3-vinylphenyl)silane, diisopropoxymethyl(3-vinylphenyl)silane, dimethoxymethyl(2-vinylphenyl)silane, diethoxymethyl(2-vinylphenyl)silane, dipropoxymethyl(2-vinylphenyl)silane, dibutoxymethyl(2-vinylphenyl)silane, diisopropoxymethyl(2-vinylphenyl)silane, dimethylmethoxy(4-vinylphenyl)silane, dimethylethoxy(4-vinylphenyl)silane, dimethylpropoxy(4-vinylphenyl)silane, dimethylbutoxy( 4-vinylphenyl)silane, dimethylisopropoxy(4-vinylphenyl)silane, dimethylmethoxy(3-vinylphenyl)silane, dimethylethoxy(3-vinylphenyl)silane, dimethylpropoxy(3-vinylphenyl)silane, dimethylbutoxy(3-vinylphenyl)silane, dimethylisopropoxy(3- vinylphenyl)silane, dimethylmethoxy(2-vinylphenyl)silane, dimethylethoxy(2-vinylphenyl)silane, dimethylpropoxy(2-vinylphenyl)silane, dimethylbutoxy(2-vinylphenyl)silane, dimethylisopropoxy(2-vinylphenyl)silane, trimethoxy(4-isopropenylphenyl) silane, triethoxy(4-isopropenylphenyl)silane, tripropoxy(4-isopropenylphenyl)silane, tributoxy(4-isopropenylphenyl)silane, triisopropoxy(4-isopropenylphenyl)silane, trimethoxy(3-isopropenylphenyl)silane, triethoxy(3-isopropenylphenyl)silane, tripropoxy(3-isopropenylphenyl)silane, tributoxy(3-isopropenylphenyl)silane, triisopropoxy(3 -isopropenylphenyl)silane, trimethoxy(2-isopropenylphenyl)silane, triethoxy(2-isopropenylphenyl)silane, tripropoxy(2-isopropenylphenyl)silane, tributoxy(2-isopropenylphenyl)silane, triisopropoxy(2-isopropenylphenyl)silane, dimethoxymethyl(4-isopropenylphenyl) )silane, diethoxymethyl(4-isopropenylphenyl)silane, dipropoxymethyl(4-isopropenylphenyl)silane, dibutoxymethyl(4-isopropenylphenyl)silane, diisopropoxymethyl(4-isopropenylphenyl)silane, dimethoxymethyl(3-isopropenylphenyl)silane, diethoxymethyl(3-isopropenylphenyl)silane , dipropoxymethyl(3-isopropenylphenyl)silane, dibutoxymethyl(3-isopropenylphenyl)silane, diisopropoxymethyl(3-isopropenylphenyl)silane, dimethoxymethyl(2-isopropenylphenyl)silane, diethoxymethyl(2-isopropenylphenyl)silane, dipropoxymethyl(2-isopropenylphenyl)silane, dibutoxymethyl (2-isopropenylphenyl)silane, diisopropoxymethyl(2-isopropenylphenyl)silane, dimethylmethoxy(4-isopropenylphenyl)silane, dimethylethoxy(4-isopropenylphenyl)silane, dimethylpropoxy(4-isopropenylphenyl)silane, dimethylbutoxy(4-isopropenylphenyl)si lan, dimethylisopropoxy(4-isopropenylphenyl)silane, dimethylmethoxy(3-isopropenylphenyl)silane, dimethylethoxy(3-isopropenylphenyl)silane, dimethylpropoxy(3-isopropenylphenyl)silane, dimethylbutoxy(3-isopropenylphenyl)silane, dimethylisopropoxy(3-isopropenylphenyl)silane, dimethylmethoxy(2-isopropenylphenyl)silane, dimethylethoxy(2-isopropenylphenyl)silane, dimethylpropoxy(2-isopropenylphenyl)silane, dimethylbutoxy(2-isopropenylphenyl)silane, dimethylisopropoxy(2-isopropenylphenyl)silane, trichloro(4-vinylphenyl)silane, trichloro( 3-vinylphenyl)silane, trichloro(2-vinylphenyl)silane, tribromo(4-vinylphenyl)silane, tribromo(3-vinylphenyl)silane, tribromo(2-vinylphenyl)silane, dichloromethyl(4-vinylphenyl)silane, dichloromethyl(3- vinylphenyl)silane, dichloromethyl(2-vinylphenyl)silane, dibromomethyl(4-vinylphenyl)silane, dibromomethyl(3-vinylphenyl)silane, dibromomethyl(2-vinylphenyl)silane, dimethylchloro(4-vinylphenyl)silane, dimethylchloro(3-vinylphenyl) silane, dimethylchloro(2-vinylphenyl)silane, dimethylbromo(4-vinylphenyl)silane, dimethylbromo(3-vinylphenyl)silane and dimethylbromine (2-vinylphenyl)silane.

Of these, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, tripropoxy(4-vinylphenyl)silane, tributoxy(4-vinylphenyl)silane, triisopropoxy(4-vinylphenyl)silane, trimethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane, tripropoxy(3-vinylphenyl)silane, tributoxy(3-vinylphenyl)silane, triisopropoxy(3-vinylphenyl)silane and trichloro(4-vinylphenyl)silane are preferred, and trimethoxy(4-vinylphenyl)silane , triethoxy(4-vinylphenyl)silane, tripropoxy(4-vinylphenyl)silane, tributoxy(4-vinylphenyl)silane and triisopropoxy(4-vinylphenyl)silane are more preferred.

[0071]

Examples of the branching agent represented by formula (2) include, but are not limited to, 1,1-bis(4-trimethoxysilylphenyl)ethylene, 1,1-bis(4-triethoxysilylphenyl)ethylene, 1,1-bis(4- tripropoxysilylphenyl)ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene, 1,1-bis(4-triisopropoxysilylphenyl)ethylene, 1,1-bis(3-trimethoxysilylphenyl)ethylene, 1,1-bis(3-triethoxysilylphenyl) ethylene, 1,1-bis(3-tripropoxysilylphenyl)ethylene, 1,1-bis(3-tripentoxysilylphenyl)ethylene, 1,1-bis(3-triisopropoxysilylphenyl)ethylene, 1,1-bis(2-trimethoxysilylphenyl)ethylene, 1,1-bis(2-triethoxysilylphenyl)ethylene, 1,1-bis(3-tripropoxysilylphenyl)ethylene, 1,1-bis(2-tripentoxysilylphenyl)ethylene, 1,1-bis(2-triisopropoxysilylphenyl)ethylene, 1, 1-bis(4-(dimethylmethoxysilyl)phenyl)ethylene, 1,1-bis(4-(diethylmethoxysilyl)phenyl)ethylene, 1,1-bis(4-(dipropylmethoxysilyl)phenyl)ethylene, 1,1-bis(4 -(dimethylethoxysilyl)phenyl)ethylene, 1,1-bis(4-(diethylethoxysilyl)phenyl)ethylene and 1,1-bis(4-(dipropylethoxysilyl)phenyl)ethylene.

Of these, 1,1-bis(4-trimethoxysilylphenyl)ethylene, 1,1-bis(4-triethoxysilylphenyl)ethylene, 1,1-bis(4-tripropoxysilylphenyl)ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene and 1,1-bis(4-triisopropoxysilylphenyl)ethylene are preferred and 1,1-bis(4-trimethoxysilylphenyl)ethylene is more preferred.

[0072]

[Conjugated Diene-Based Polymer Production Method]

The method for producing a conjugated diene based polymer of the present embodiment comprises the step of polymerizing/branching at least a conjugated diene compound in the presence of an organolithium compound to obtain a conjugated diene based polymer having a branched main chain structure using at least any one of the various branching agents described above; and a step of linking the conjugated diene based polymer using a binder and/or a step of modifying the conjugated diene based polymer with a modifier having a nitrogen atom containing group.

The conjugated diene-based polymer contained in the modified conjugated diene-based polymer can be any of a homopolymer of one conjugated diene compound, a polymer namely a copolymer, various kinds of conjugated diene compounds, and a copolymer of a conjugated diene compound and an aromatic vinyl compound.

[0073]

(Polymerization/branching stage)

In the polymerization/branching step in the conjugated diene polymer production method of the present embodiment, an organolithium compound such as an organolithium monolithium compound is used as a polymerization initiator so as to polymerize at least a conjugated diene compound, and a branching agent is added in order to obtain a polymer based on a conjugated diene having a branched main chain structure.

In the polymerization step, the polymerization is preferably performed by a growth reaction by a living anionic polymerization reaction, and thus a conjugated diene-based polymer having an active end can be obtained. Thereafter, also in the branching step using the branching agent, the main chain branching can be suitably controlled, and a modified conjugated diene-based polymer having a high degree of modification can be obtained by continuing polymerization at the active end after the main chain branching.

[0074]

<Polymerization initiator>

An organolithium compound is used as the polymerization initiator, and at least an organolithium monolithium compound is preferably used.

An example of an organolithium monolithium compound includes, but is not limited to, a low molecular weight organomonolithium compound or a soluble oligomer.

With regard to the method of bonding between an organic group and its lithium, examples of the monolithium compound include a compound having a carbon-lithium bond, a compound having a nitrogen-lithium bond, and a compound having a tin-lithium bond.

[0075]

The amount of the organolithium monolithium compound to be used as the polymerization initiator is preferably determined based on the molecular weight of the target conjugated diene based polymer.

The ratio of the amount of monomer used, such as a conjugated diene compound, to the amount of polymerization initiator used refers to the degree of polymerization of the target conjugated diene-based polymer. In other words, it tends to refer to number average molecular weight and/or weight average molecular weight.

Accordingly, to increase the molecular weight of the conjugated diene polymer, adjustment can be made to decrease the amount of polymerization initiator, and to decrease the molecular weight, adjustment can be made to increase the amount of polymerization initiator.

[0076]

From the viewpoint of being used as one of the methods for introducing a nitrogen atom into a conjugated diene-based polymer, the organomonolithium compound is preferably an alkyllithium compound having a substituted amino group or a dialkylaminolithium.

In this case, a polymer based on a conjugated diene is obtained, having an amino group nitrogen atom at the initial end of polymerization.

[0077]

A substituted amino group refers to an amino group having no active hydrogen or having a structure in which the active hydrogen is protected.

Examples of the alkyl lithium compound containing an amino group having no active hydrogen include, but are not limited to, 3-dimethylaminopropyllithium, 3-diethylaminopropyllithium, 4-(methylpropylamino)butyllithium, and 4-hexamethyleneiminobutyllithium.

Examples of the alkyllithium compound containing an amino group having a structure in which the active hydrogen is protected include, but are not limited to, 3-bistrimethylsilylaminopropyllithium and 4-trimethylsilylmethylaminobutyllithium.

[0078]

Examples of dialkylaminolithium include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium di-n-hexylamide, lithium diheptylamide, lithium diisopropylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium ethylpropylamide , lithium ethylbutylamide, lithium ethylbenzylamide, lithium methylphenethylamide, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium morpholide, 1-lithium azacyclooctane, 6-lithium-1,3,3-trimethyl-6-azabicyclo[3.2.1]octane , and 1-lithium-1,2,3,6-tetrahydropyridine.

[0079]

Such an organolithium monolithium compound having a substituted amino group can be reacted with a small amount of a polymerizable monomer such as 1,3-butadiene, isoprene or styrene to be used as an oligomer monolithium compound soluble in normal hexane or cyclohexane.

[0080]

From the point of view of industrial availability and controllability of the polymerization reaction, the monolithium organic compound is preferably an alkyl lithium compound. In this case, a conjugated diene-based polymer having an alkyl group at the initial polymerization end can be obtained.

Examples of the alkyl lithium compound include, but are not limited to, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilben lithium.

From the point of view of industrial availability and controllability of the polymerization reaction, the alkyl lithium compound is preferably n-butyl lithium or sec-butyl lithium.

[0081]

One of these monolithium compounds may be used alone, or two or more of them may be used together. Alternatively, another organometallic compound may be used with them.

Examples of such other organometallic compound include alkaline earth metal compounds, alkali metal compounds, as well as other organometallic compounds.

Examples of alkaline earth metal compounds include, but are not limited to, organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Other examples include compounds of alkoxides, sulfonates, carbonates and amides of alkaline earth metals.

Examples of organic magnesium compounds include dibutyl magnesium and ethyl butyl magnesium. Examples of other organometallic compounds include organic aluminum compounds.

[0082]

Examples of the polymerization reaction mode used in the polymerization step include, but are not limited to, batch and continuous polymerization reaction modes.

In continuous mode, one reactor or two or more connected reactors can be used. As a reactor for continuous operation, for example, a vessel or tubular reactor equipped with a stirrer can be used. In continuous mode, monomer, inert solvent and polymerization initiator are continuously fed into the reactor, a polymer solution containing polymer is obtained in the reactor, and this polymer solution is continuously discharged from the reactor.

As a batch reactor, for example, a tank reactor equipped with a stirrer is used. In a batch mode, preferably monomer, an inert solvent and a polymerization initiator are fed into the reactor, the monomer is continuously or intermittently additionally fed as necessary during the polymerization, a polymer solution containing the polymer is obtained in the reactor, and this polymer solution is discharged from the reactor after completion of the polymerization.

In the process for producing a conjugated diene based polymer of the present embodiment, in order to obtain a conjugated diene based polymer having a high active end ratio, a continuous method is preferably used in which the polymer is continuously discharged to be fed to the next reaction after a short period of time.

[0083]

In the polymerization step of the conjugated diene based polymer, the polymerization is preferably carried out in an inert solvent.

Examples of the inert solvent include hydrocarbon-based solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specific examples of the hydrocarbon-based 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; as well as a mixture of any of them.

Allene and acetylene impurities are preferably treated with an organometallic compound before the solvent is supplied to the polymerization reaction, because a conjugated diene-based polymer having a high active end concentration can thus be obtained, and accordingly a modified conjugated diene-based polymer having a high degree of modification can be obtained.

[0084]

A polar compound may be added during the polymerization step. Thus, an aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound, and a polar compound can also be used as a vinylating agent to control the microstructure of the conjugated diene portion. In addition, it can be advantageous, for example, to accelerate the polymerization reaction.

[0085]

Examples of the polar compound include, but are not limited to, ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis(2-oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine and quinuclidine; alkali metal alkoxide compounds such as potassium t-amylate, potassium t-butoxide, sodium t-butoxide and sodium amylate; as well as phosphine compounds such as triphenylphosphine.

One of these polar compounds may be used alone, or two or more of them may be used together.

[0086]

The amount of the polar compound to be used is not particularly limited, but may be selected according to the purpose and the like, and is preferably 0.01 mol or more and 100 mol or less per mol of polymerization initiator.

Such a polar compound (vinylating agent) can be used as a microstructure modifier for the conjugated diene portion of the conjugated diene based polymer, in an appropriate amount according to the desired amount of bound vinyl.

There is a tendency that many polar compounds simultaneously have an effective randomizing effect in the copolymerization of the conjugated diene compound and the aromatic vinyl compound, and can be used as a modifier for the distribution of the aromatic vinyl compound and the amount of the styrene block.

As a method for randomizing a conjugated diene compound and an aromatic vinyl compound, for example, the method described in Japanese Patent Laid-Open No. 59-140211, in which the copolymerization reaction is started with all of styrene and part of 1,3-butadiene, and the remainder of 1 ,3-Butadiene is intermittently added during the copolymerization reaction.

[0087]

In the polymerization step, the temperature at which the living anionic polymerization proceeds is preferably maintained, and from the viewpoint of productivity, this temperature is more preferably 0°C or more and 120°C or less. If the polymerization temperature is in this range, there is a tendency that the reactive amount of the modifier reacted with the active end can be sufficiently achieved after completion of the polymerization. The polymerization temperature is even more preferably 50°C or more and 100°C or less.

[0088]

In the conjugated diene-based polymer production method of the present embodiment, the amount of branching agent added in the branching step to form a branched main chain structure is not particularly limited, but may be selected according to the purpose and the like, and is preferably 0.03 mol or more and 0.5 mol or less, more preferably 0.05 mol or more and 0.4 mol or less, and even more preferably 0.01 mol or more and 0.25 mol or less per mol of polymerization initiator.

The branching agent may be used in a suitable amount according to the number of branching points of the main chain branching structure of the conjugated diene portion of the conjugated diene-based target polymer.

[0089]

The time of adding the branching agent in the branching step is not particularly limited, and may be selected according to the purpose and the like, and from the viewpoints of improving the absolute molecular weight of the conjugated diene-based polymer and improving the degree of modification, is the time after adding the polymerization initiator when the raw material conversion ratio is preferably 20% or more, more preferably 40% or more, even more preferably 50% or more, even more preferably 65% or more, and most preferably 75% or more.

After the branching agent is added, the desired feedstock may be further added in order to continue the polymerization step after branching, or the above process may be repeated.

The amount of added monomer is not particularly limited, and from the viewpoint of improving the degree of modification of the conjugated diene-based polymer, it is preferably 5% or more, more preferably 10% or more, even more preferably 15% or more, even more preferably 20% or more. , and most preferably 25% or more based on the total number of conjugated diene-based monomers, for example, on the total amount of butadiene used in the polymerization stage.

[0090]

The resulting conjugated diene based polymer before the modification reaction by the polymerization/branching step in the conjugated diene based polymer production method of the present embodiment has a Mooney viscosity at 110°C, preferably 10 or more and 150 or less, more preferably 15 or more and 140 or less, and even more preferably 20 or more and 130 or less.

If the Mooney viscosity is in this range, the conjugated diene-based polymer of the present embodiment tends to have excellent workability and abrasion resistance.

[0091]

The conjugated diene-based polymer of the present embodiment may be a polymer of a conjugated diene monomer and a branching agent, or may be a copolymer of a conjugated diene monomer, a branching agent and another monomer.

For example, when the conjugated diene monomer is butadiene or isoprene, and this diene monomer is polymerized with a branching agent containing an aromatic vinyl moiety, the polymer chain is what is called polybutadiene or polyisoprene, and a polymer is obtained containing a structure derived from an aromatic vinyl in branched part. With such a structure, the linearity of each polymer chain as well as the crosslink density after vulcanization can be improved, resulting in an effect of improving the abrasion resistance of the polymer. Therefore, such a resin is suitably used for tires, resin modification, vehicle interior/exterior parts, damping rubber, shoes, and the like.

When a conjugated diene-based polymer is used for a tire tread, a copolymer of a conjugated diene monomer, an aromatic vinyl monomer and a branching agent is suitably used, and in the copolymer used in this application, the amount of the conjugated diene is preferably 40 mass% or more and 100 mass .% or less, and more preferably 55 wt.% or more and 80 wt.% or less.

In addition, the amount of bonded aromatic vinyl in the conjugated diene-based polymer of the present embodiment is not particularly limited, and is preferably 0 wt% or more and 60 wt% or less, and more preferably 20 wt% or more and 45 wt%. % or less.

When the amounts of bound conjugated diene and bound aromatic vinyl are in the above-described ranges, the balance between low hysteresis loss property and wet slip resistance, abrasion resistance and fracture characteristics in the form of a vulcanizate tend to be more excellent.

Here, the amount of bound aromatic vinyl can be measured according to the UV absorption of the phenyl group, and based on the amount thus obtained, the amount of bound conjugated diene can also be obtained. In particular, this amount is measured in accordance with the method which will be described later in the examples.

[0092]

In the conjugated diene-based polymer of the present embodiment, the amount of bound vinyl in the conjugated diene bound block is not particularly limited, and is preferably 10 mol% or more and 75 mol% or less, and more preferably 20 mol% or more and 65 mol .% or less.

If the amount of bonded vinyl is in the above-described range, the balance between low hysteresis loss property and wet skid resistance, abrasion resistance and fracture toughness in the form of a vulcanizate tend to be more excellent.

Here, if the modified diene-based polymer is a butadiene-styrene copolymer, the amount of bound vinyl (amount of 1,2-bond) in the butadiene bond unit can be obtained by the Hampton method (R. R. Hampton, Analytical Chemistry, 21, 923 (1949)) . In particular, it can be measured by the method described in the examples below.

[0093]

With regard to the microstructure of the conjugated diene based polymer, if the amounts of the above bonds in the conjugated diene based polymer of the present embodiment are in the above-described ranges, and the glass transition temperature of the conjugated diene based polymer is -70°C or more and -15°C or less, may a vulcanizate having a more excellent balance between low hysteresis loss property and wet skid resistance can be obtained.

The glass transition temperature is defined as the peak (inflection point) of a differential DSC curve obtained by recording the DSC curve during temperature increase over a given temperature range in accordance with ISO 22768:2006. In particular, it can be measured in accordance with the method described in the examples below.

[0094]

If the conjugated diene-based polymer of the present embodiment is a conjugated diene-aromatic vinyl copolymer, it preferably contains little or no blocks in which 30 or more aromatic vinyl blocks are connected in a chain. More specifically, if the conjugated diene-based polymer of the present embodiment is a butadiene-styrene copolymer, using a known method in which the copolymer is cleaved by the Kolthoff method (described in I. M. Kolthoff, et al., J. Polym. Sci. 1, 429 ( 1946)) to analyze the amount of polystyrene insoluble in methanol, blocks each of which 30 or more aromatic vinyl blocks are connected in a chain are preferably 5.0 mass% or less, and more preferably 3.0 mass% or less by the total amount of conjugated diene-based polymer.

[0095]

From the viewpoint of improving fuel efficiency, if the conjugated diene-based polymer of the present embodiment is a conjugated diene-aromatic vinyl copolymer, most of the aromatic vinyl block is preferably present alone.

In particular, if the conjugated diene-based polymer of the present embodiment is a butadiene-styrene copolymer, when the conjugated diene-based polymer is cleaved using an ozonolysis method known as the Tanaka method (see Tanaka et al., Polymer, 22, 1721 (1981 )) to analyze the distribution of styrene in a chain by GPC, it is preferable that the amount of isolated styrene relative to the total amount of bound styrene is 40 mass% or more, and that the amount of a styrene chain structure consisting of 8 or more chained styrene blocks is 5.0 mass% or less.

In this case, the resulting vulcanized rubber tends to achieve excellent performance, in particular low hysteresis loss.

[0096]

(Reaction step)

In the production method of the conjugated diene based polymer of the present embodiment, the step of linking the active end of the conjugated diene based polymer obtained by the polymerization/branching step with a binder such as a tri- or higher functional reactive compound and/or the step of modifying it is carried out. a modifier having a nitrogen atom containing group (preferably a binder having a nitrogen atom containing group).

Hereinafter, the coupling step and/or the active end modification step will be referred to as the reaction step.

In the reaction step, one end of the active end of the conjugated diene-based polymer undergoes a modification reaction with a binder or a nitrogen atom-containing group, and thus a modified conjugated diene-based polymer is obtained.

[0097]

<Binder>

The binder used in the reaction step of the conjugated diene polymer production method of the present embodiment may have any structure, as long as it is a three or more functional reactive compound, and is preferably a three or more functional reactive compound. having a silicon atom, and more preferably having at least 4 functional groups containing silicon. A more preferred binder is a compound in which at least one silicon atom constitutes an alkoxysilyl group or a silanol group having 1-20 carbon atoms. Examples of such a binder include tetramethoxysilane and tetraethoxysilane.

[0098]

<Modifier>

Examples of the modifier include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-tripropoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy -1-aza-2-silacyclopentane)propyl]amine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2 -azacyclopentane)propyl]-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-methyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, bis( 3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1 ,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3- bisaminomethylcyclohexane, tetrakis(3-trimethoxysilylpropyl)-1,6-hexamethylenediamine, pentakis(3-trimethoxysilylpropyl)-diethylenetriamine, tris(3-trimethoxysilylpropyl)-methyl-1,3-propand iamine, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane) )propyl]silane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, tris[3-(2,2-dimethoxy-1-aza-2 -silacyclopentane)propyl]-[3-(1-methoxy-1-trimethylsilyl-1-sila-2-azacyclopentane)propyl]silane, 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane )ethoxy]silyl-1-trimethoxysilylpropane, 1-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexane, 1 -[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexane, 3,4,5-tris(3-trimethoxysilylpropyl)- cyclohexyl-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]ether, (3-trimethoxysilylpropyl)phosphate, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1- aza-2-silacyclopentane)propyl] phosphate, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)phosphate and tris[3-(2,2-dimethoxy- one- aza-2-silacyclopentane)propyl]phosphate.

[0099]

The modifier preferably contains a compound represented by any of the following general formulas (A) - (C):

[0100]

[0101]

where each of R ¹ - R ⁴ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, R ⁵ represents an alkylene group having 1-10 carbon atoms, R ⁶ represents an alkylene group, having 1-20 carbon atoms, m is an integer 1 or 2, n is an integer 2 or 3, (m+n) is 4 or more, and each of R ¹ - R ⁴ if present in the plural, respectively is independent.

[0102]

[0103]

where each of R ¹ - R ⁶ independently represents an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, each of R ⁷ - R ⁹ independently represents an alkylene group having 1-20 carbon atoms, m, n and l each independently represents an integer 1-3, (m+n+l) is 4 or more, and each of R ¹ - R ⁶ if present in the plural, respectively, is independent.

[0104]

[0105]

in which each of R ¹² - R ¹⁴ independently represents a single bond or an alkylene group having 1-20 carbon atoms, each of R ¹⁵ - R ¹⁸ and R ²⁰ independently represents an alkyl group having 1-20 carbon atoms, each of R ¹⁹ and R ²² independently represents an alkylene group having 1-20 carbon atoms, R ²¹ represents an alkyl group or a trialkylsilyl group having 1-20 carbon atoms, m represents an integer 1-3, p is 1 or 2, each of R ¹² - R ²² , m and p, if present in the plural, are respectively independent, and may be the same or different, i represents an integer from 0 to 6, j represents an integer from 0 to 6, k represents an integer from 0 to 6, (i+j+k) is 4-10, and A represents a hydrocarbon group having 1-20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, an atom nitrogen, silicon atom, sulfur atom and phosphorus atom, and not having active hydrogen.

[0106]

Examples of the modifier represented by formula (A) include, but are not limited to, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3- triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-(4-trimethoxysilylbutyl)-1-aza-2-silacyclohexane, 2,2-dimethoxy-1-(5-trimethoxysilylpentyl)-1-aza -2-silacycloheptane, 2,2-dimethoxy-1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane, 2 -methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-methoxy -1-methyl-1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane; and 2-ethoxy-2-ethyl-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane.

Among them, from the viewpoint of reactivity and interaction between the functional group of the modifier and the inorganic filler such as silica, and also from the viewpoint of workability, it is preferable that m is 2 and n is 3. In particular, 2.2 -dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane; and 2,2-diethoxy-1-(3-triethoxysilylpropyl)-1-aza-2-silacyclopentane.

[0107]

The reaction temperature, reaction time, and the like causing the modifier represented by formula (A) to react with the active end of the polymer are not particularly limited, and 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 of the compound used as the modifier represented by formula (A) is preferably 0.6 or more and 3.0 or less, more preferably 0.8 or more and 2.5 or less, and even more preferably 0.8 or more and 2.0 or less of the moles of the alkali metal compound and/or the alkaline earth metal compound of the polymerization initiator added. In order for the modified conjugated diene-based polymer thus obtained to have a sufficient degree of modification and molecular weight, as well as a branched structure, the total number of moles is preferably 0.6 or more of this value, and the branched polymer component is preferably obtained by linking the ends of the polymer to improve workability, and furthermore, from the point of view of the cost of the modifier, the total number of moles is preferably 3.0 or less of the specified value.

More specifically, the number of moles of the polymerization initiator is preferably 3.0 or more, and more preferably 4.0 or more of the moles of the modifier.

[0108]

Examples of the modifier represented by formula (B) include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, tris(3-methyldimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-methyldiethoxysilylpropyl)amine, tris (trimethoxysilylmethyl)amine, tris(2-trimethoxysilylethyl)amine and tris(4-trimethoxysilylbutyl)amine.

Among them, from the viewpoint of reactivity and interaction between the functional group of the modifier and the inorganic filler such as silica, and also from the viewpoint of workability, it is preferable that each of n, m, and l be 3. Specific preferred examples include tris (3-trimethoxysilylpropyl)amine; and tris(3-triethoxysilylpropyl)amine.

[0109]

The reaction temperature, reaction time, and the like causing the modifier represented by the formula (B) to react with the active end of the polymer are not particularly limited, and 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 mole of the alkoxy group bonded to the silyl group of the compound used as the modifier represented by formula (B) is preferably 0.6 or more and 3.0 or less, more preferably 0.8 or more and 2.5 or less, and even more preferably 0.8 or more and 2.0 or less of the number of moles of lithium contained in the added polymerization initiator. In order for the modified conjugated diene-based polymer to have a sufficient degree of modification and molecular weight, as well as a branched structure, the total number of moles is preferably 0.6 or more of the specified value, and the branched polymer component is preferably obtained by linking the ends of the polymer to improve processability. , and in addition, from the point of view of the cost of the modifier, the total number of moles is preferably 3.0 or less of the specified value.

More specifically, the number of moles of the polymerization initiator is preferably 4.0 or more, and more preferably 5.0 or more of the moles of the modifier.

[0110]

In formula (C), A is preferably represented by any of the following general formulas (II) to (V):

[0111]

[0112]

where B ¹ represents a single bond or a hydrocarbon group having 1-20 carbon atoms, and represents an integer 1-10, and B ¹ if present in the plural, respectively, is independent;

[0113]

[0114]

where B ² represents a single bond or hydrocarbon group having 1-20 carbon atoms, B ³ represents an alkyl group having 1-20 carbon atoms, and represents an integer 1-10, and each of B ² and B ³ if present in the plural, is accordingly independent;

[0115]

[0116]

where B ⁴ represents a single bond or a hydrocarbon group having 1-20 carbon atoms, and represents an integer of 1-10, and B ⁴ if present in the plural, respectively, is independent; and

[0117]

[0118]

where B ⁵ represents a single bond or a hydrocarbon group having 1-20 carbon atoms, and represents an integer of 1-10, and B ⁵ if present in the plural, respectively, is independent.

[0119]

Examples of the modifier represented by formula (C) in which A is represented by formula (II) include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy -1-aza-2-silacyclopentane)propyl]amine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)amine, tris[3-(2.2 -dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3-ethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silasilylopentane)propyl] amine, bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-(3-triethoxysilylpropyl)amine, tris[3-(2,2-diethoxy-1-aza-2-silacyclopentane) propyl]amine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine , bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tris[3-(2,2-dimethoxy-1-aza -2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)1,3-propanediamine, tetrakis [3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila- azacyclopentane)propyl]-1,3-propanediamine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy-2-trimethylsilyl -1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-[3-( 1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-triethoxysilylpropyl)-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[3-( 2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, bis(3-triethoxysilylpropyl)-bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl ]-1,3-propanediamine, tris[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-(3-triethoxysilylpropyl)-1,3-propanediamine, tetrakis[3-(2,2 -diethoxy-1-aza- 2-silacyclopentane)propyl]-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, bis (3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]- 1,3-propanediamine, bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-(3-triethoxysilylpropyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila- 2-azacyclopentane)propyl]-1,3-propanediamine, tris[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila -2-azacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2- silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tris[3- (2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tetrakis [3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila- 2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-methoxy-2 -trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-[3 -(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2,2-dimethoxy-1-aza-2-cyclopentane)propyl]-[ 3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tetrakis(3-triethoxysilylpropyl)-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[3 -(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane )propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-(3- triethoxysilylpropyl)-1,3-propanediamine, tetrakis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tris(3-triethoxysilylpropyl)-[3-(1- ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl] -[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl ]-(3-triethoxysilylpropyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tris[3-(2,2-diethoxy-1- aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, tetrakis(3-trimethoxysilylpropyl)-1,6-hexamethylenediamine and pentakis(3-trimethoxysilylpropyl)-diethylenetriamine.

[0120]

Examples of the modifier represented by formula (C) in which A is represented by formula (III) include, but are not limited to, tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-trimethoxysilylpropyl)-[3 -(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-methyl-1,3-propanediamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-( 3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, tris(3-triethoxysilylpropyl)-methyl-1,3-propanediamine, bis(2-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2 -silacyclopentane)propyl]-methyl-1,3-propanediamine, bis[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-(3-triethoxysilylpropyl)-methyl-1,3-propanediamine, N ¹ ,N ¹ '-(propane-1,3-diyl)bis(N ¹ -methyl-N ³ ,N ³ -bis(3-(trimethoxysilyl)propyl)-1,3-propanediamine) and N ¹ -( 3-(bis(3-(trimethoxysilyl)propyl)amino)propyl)-N ¹ -methyl-N ³ -(3-(methyl(3-(trimethoxysilyl)propyl)amino)propyl)-N ³ -(3-( trimethoxysilyl)propyl)-1,3-propanediamine.

[0121]

Examples of the modifier represented by formula (C) in which A is represented by formula (IV) include, but are not limited to, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, tris [3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)silane, tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]- [3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]silane, bis(3-trimethoxysilylpropyl)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]silane, (3-trimethoxysilyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]silane, bis[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)-bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, tris (3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, bis(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila -2-azacyclopentane)propyl]-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane, bis[3-(1-methoxy-2-trimeth ylsilyl-1-sila-2-azacyclopentane)propyl]-bis(3-trimethoxysilylpropyl)silane and bis(3-trimethoxysilylpropyl)-bis[3-(1-methoxy-2-methyl-1-sila-2-azacyclopentane)propyl ]silane.

[0122]

Examples of the modifier represented by formula (C) in which A is represented by formula (V) include, but are not limited to, 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl -1-(2,2-dimethoxy-1-aza-2-silacyclopentane)propane; and 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane.

[0123]

In formula (C), A is preferably represented by formula (II) or formula (III) and k is 0 (zero).

Such a modifier is usually readily available and tends to give the resulting conjugated diene polymer of the present embodiment a more excellent abrasion resistance and low hysteresis loss property in the form of a vulcanizate.

Examples of such a modifier include, but are not limited to, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3-trimethoxysilylpropyl)amine, tris( 3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis[3-(2,2-dimethoxy -1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl) -methyl-1,3-propanediamine; and bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trismethoxysilylpropyl)-methyl-1,3-propanediamine.

[0124]

In formula (C), it is more preferred that A is represented by formula (II) or formula (III), and that k is 0 (zero) and an integer of 2-10 in formula (II) or formula (III).

Thus, the abrasion resistance and the low hysteresis loss property of the vulcanizate form tend to become more excellent.

Examples of such a modifier include, but are not limited to, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3- propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane and N ¹ -(3-(bis(3-(trimethoxysilyl)propyl)amino)propyl)-N ¹ -methyl-N ³ -(3-(methyl( 3-(trimethoxysilyl)propyl)amino)propyl)-N ³ -(3-(trimethoxysilyl)propyl)-1,3-propanediamine.

[0125]

The amount of the compound represented by formula (C) added as a modifier can be adjusted to cause the modifier to react with the conjugated diene based polymer so that the number of moles of the modifier relative to the number of moles of the conjugated diene based polymer is in the desired stoichiometric ratio, and thus the desired star-shaped polymeric branching structure can be achieved.

In particular, the number of moles of the conjugated diene-based polymer is preferably 5.0 or more, and more preferably 6.0 or more relative to the number of moles of the modifier.

In this case, in formula (C), the number of functional groups ((m - 1) x i+p x j+k) of the modifier is preferably an integer of 5 to 10, and more preferably 6 to 10.

[0126]

In the modified conjugated diene-based polymer of the present embodiment, the proportion of the polymer containing the modifying group in the conjugated diene-based polymer is expressed as the degree of modification.

In the conjugated diene-based polymer of the present embodiment, the degree of modification is preferably 60 wt% or more, more preferably 65 wt% or more, even more preferably 70 wt% or more, still more preferably 75 wt% or more, still more preferably 80 wt.% or more, and particularly preferably 82 wt.% or more.

If the degree of modification is 60% by mass or more, there is a tendency that workability in the vulcanizate mold is excellent, and abrasion resistance and low hysteresis loss property in the vulcanizate mold are more excellent.

[0127]

In the present embodiment, the condensation reaction step in the presence of a condensation accelerator may be performed after the reaction step or before the reaction step.

[0128]

The conjugated diene-based polymer of the present embodiment may be hydrogenated in its conjugated diene portion.

The method for hydrogenating the conjugated diene portion of the modified conjugated diene based polymer of the present embodiment is not particularly limited, and any known method may be used.

As a suitable hydrogenation method, a method in which hydrogenation is performed by blowing hydrogen gas into a polymer solution in the presence of a catalyst can be used.

Examples of the catalyst include heterogeneous catalysts such as a noble metal catalyst supported on a porous inorganic substance; homogeneous catalysts such as a catalyst obtained by reacting a dissolved salt of nickel, cobalt, and the like. with an organoaluminum and the like, as well as a catalyst using a metallocene such as a titanocene. Among these catalysts, from the point of view of selecting moderate hydrogenation conditions, it is preferable to use a titanocene catalyst.

In addition, the hydrogenation of an aromatic group can be carried out by using a noble metal catalyst.

[0129]

Examples of a hydrogenation catalyst include, but are not limited to, (1) a supported heterogeneous hydrogenation catalyst obtained by supporting a metal such as Ni, Pt, Pd, or Ru on carbon, silica, alumina, or diatomite, (2) a Ziegler catalyst using organic acid salts of Ni, Co, Fe, Cr and the like, or transition metal salts such as an acetylacetone salt and a reducing agent such as an organoaluminum compound, and (3) organometallic complex compounds such as an organometallic compound of Ti, Ru , Rh or Zr. In addition, examples of the hydrogenation catalyst include known hydrogenation catalysts described in, 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, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-9041, and Japanese Patent Application Pending No. 8-109219. A preferred hydrogenation catalyst is a reaction mixture of a titanocene compound and a reducing organometallic compound.

[0130]

In the production method of the conjugated diene-based polymer of the present embodiment, a deactivator, a neutralizing agent, and the like. may optionally be added to the resulting polymer solution after the reaction step.

Examples of the deactivator include, but are not limited to, water; as well as 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 versatic acid (a mixture of highly branched carboxylic acids having 9-11 carbon atoms, mainly 10 carbon atoms); and an aqueous solution of an inorganic acid and carbon dioxide gas.

[0131]

A rubber stabilizer is preferably added to the conjugated diene-based polymer of the present embodiment from the viewpoint of preventing gelation after polymerization and improving processing stability.

As a stabilizer for rubber, any known stabilizer may be used, without being limited to the following, and preferred examples include antioxidants such as 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3-( 4'-hydroxy-3',5'-di-tert-butylphenol)propionate; and 2-methyl-4,6-bis[(octylthio)methyl]phenol.

[0132]

(Filled polymer based on conjugated diene)

The filled conjugated diene polymer of the present embodiment comprises the conjugated diene based polymer of the present embodiment described above and at least any substance selected from the group consisting of a filling oil, a latex, and a resin.

It should be noted that the filled conjugated diene polymer encompasses not only the filled conjugated diene based polymer containing oil, but also containing oil-free liquid polybutadiene, or any of various resins.

Thus, the processability of the conjugated diene-based polymer can be further improved.

A preferred example of a method for adding an extender oil to a conjugated diene polymer includes, but is not limited to, a method in which an extender oil is added to a stirred conjugated diene polymer solution and the resulting expanded polymer solution is desolvated.

Examples of the extender oil include aromatic oil, naphthenic oil, and paraffin oil. Among these oils, an alternative flavor oil containing 3 wt% or less of a polycyclic aromatic (PCA) component in accordance with IP 346 is preferable in terms of environmental safety, oil bleed prevention, and wet grip performance. Examples of the alternative flavor oil include including TDAE (treated aromatic extract distillates), MES (mild extraction solvate) and the like mentioned in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), as well as RAE (residual aromatic extracts).

Examples of the latex include, but are not limited to, liquid polybutadiene and liquid styrene butadiene rubber.

Examples of the resin include, but are not limited to, aromatic petroleum resin, coumarone-indene resin, terpene resin, rosin derivatives (including wood oil resin), tall oil, tall oil derivatives, rosin ester resin, natural or synthetic terpene resin, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, mixed aliphatic/aromatic hydrocarbon resin, coumarin-indene resin, phenolic resin, p-tert-butylphenol acetylene resin, phenol formaldehyde resin, xylene formaldehyde resin, monoolefin oligomer, diolefin oligomer, aromatic hydrocarbon resin, resin aromatic oil resin, hydrogenated aromatic hydrocarbon resin, cyclic aliphatic hydrocarbon resin, hydrogenated hydrocarbon resin, hydrocarbon resin, hydrogenated wood oil resin, hydrogenated oil resin, as well as an ester of hydrogenated oil resin and a single-functional or multifunctional functional alcohol.

One of these resins may be used alone, or two or more of them may be used together. During hydrogenation, all unsaturated groups may be hydrogenated, or some of them may be left unhydrogenated.

The added amount of at least any substance selected from the group consisting of extender oil, latex and resin is not limited, and is preferably 1-60 ppm, more preferably 10-60 ppm, and even more preferably 15-37.5 m.h. per 100 m.h. the conjugated diene based polymer of the present embodiment.

[0133]

(Desolvation step)

As a method for producing the conjugated diene-based polymer of the present embodiment from the polymer solution, any of the known methods can be used. Examples of the method include a method in which the conjugated diene based polymer is filtered after steaming off the solvent and the like, and the resultant residue is dehydrated and dried to obtain a conjugated diene based polymer, a method in which the solution is concentrated into washing tank, and the resultant residue is subjected to degassing using a curved extruder or the like, and a method in which the solution is directly degassed using a drum dryer or the like.

[0134]

[Rubber composition]

The rubber composition of the present embodiment contains a rubber component and 5.0 m.h. or more and 150 m.ch. or less filler per 100 m.h. rubber component.

From the viewpoints of fuel efficiency, workability, and improvement in abrasion resistance, the rubber component contains, by total amount (100 mass%) of the rubber component, 10 mass% or more of the above-described conjugated diene based polymer of the present embodiment or the filled conjugated diene based polymer of the present embodiment .

[0135]

The filler preferably contains an inorganic filler based on silica.

If the silica-based inorganic filler is dispersed in the rubber composition of the present embodiment, the rubber composition acquires more excellent workability when used to make a vulcanizate, as well as a more excellent balance between low hysteresis loss property and wet skid resistance, abrasion resistance, and fracture toughness. in the form of a vulcanizate.

In addition, when the rubber composition of the present embodiment is to be used in application to a vulcanized rubber such as a tire, a vehicle component such as a damping rubber, or a shoe, it preferably contains a silica-based inorganic filler.

[0136]

In the rubber composition of the present embodiment, a rubbery polymer other than the conjugated diene based polymer of the present embodiment (hereinafter simply referred to as "rubber polymer") may be contained in combination with the conjugated diene based polymer of the present embodiment.

Examples of such a rubbery polymer include, but are not limited to, a polymer based on a conjugated diene or a hydrogenated product thereof, a random copolymer of a compound based on a conjugated diene and a vinyl aromatic compound or a hydrogenated product thereof, a block copolymer of a compound based on a conjugated diene and a vinyl aromatic compound. or its hydrogenated product, non-diene polymer and natural rubber.

Specific examples of the rubbery polymer include, but are not limited to, butadiene rubber or a hydrogenated product thereof, isoprene rubber or a hydrogenated product thereof, styrene-based elastomers such as styrene-butadiene rubber or a hydrogenated product thereof, and a styrene-butadiene block copolymer. or a hydrogenated product thereof, a styrene-isoprene block copolymer or a hydrogenated product thereof, and acrylonitrile butadiene rubber or a hydrogenated product thereof.

[0137]

Examples of the non-diene polymer include, but are not limited to, olefin-based elastomers such as ethylene propylene rubber, ethylene propylene diene rubber, ethylene butene diene rubber, ethylene butene rubber, ethylene hexene rubber, and ethylene octene rubber. rubber, butyl rubber, brominated butyl rubber, acrylic rubber, fluororubber, silicone rubber, chloropolyethylene rubber, epichlorohydrin rubber, α,β-unsaturated nitrile-acrylic acid conjugated diene rubber, urethane rubber, and polysulfide rubber.

[0138]

Examples of natural rubber include, but are not limited to, smoked sheets RSS Nos. 3-5, SMR, and epoxidized natural rubber.

[0139]

The various rubbery polymers described above may be in the form of a modified rubber endowed with a functional group having a polarity such as a hydroxyl group or an amino group. For use in the tire, butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber and butyl rubber are preferably used.

[0140]

The weight average molecular weight of the rubbery polymer is preferably 2,000 or more and 2,000,000 or less, and more preferably 5,000 or more and 1,500,000 or less, from the point of view of the balance between performance and processing properties. In addition, a rubbery polymer having a low molecular weight can be used, namely that which is called a latex. One of these rubbery polymers may be used alone, or two or more of them may be used together.

[0141]

In the rubber composition containing the conjugated diene based polymer of the present embodiment and the rubbery polymer, the weight ratio of the conjugated diene based polymer of the present embodiment and the rubbery polymer (conjugated diene based polymer of the present embodiment/rubberlike polymer) is preferably 10/90 or more and 100/0 or less, more preferably 20/80 or more and 90/10 or less, and even more preferably 50/50 or more and 80/20 or less.

Accordingly, the rubber component contained in the rubber composition contains 100 m.h. the rubber component of the conjugated diene polymer of the present embodiment in an amount of preferably 10 m.h. or more and 100 m.ch. or less, more preferably 20 m.h. or more and 90 m.h. or less, and even more preferably 50 m.h. or more and 80 m.h. or less.

If the ratio (conjugated diene based polymer of the present embodiment/rubber polymer) is in the above-described range in the form of a vulcanizate, the balance between low hysteresis loss property and wet skid resistance is excellent, abrasion resistance is excellent, and fracture toughness is good. .

[0142]

Examples of the filler contained in the rubber composition of the present embodiment include, but are not limited to, silica-based inorganic filler, carbon black, metal oxide, and metal hydroxide. Of these, silica-based inorganic filler is preferable.

One of these excipients may be used alone, or two or more of them may be used together.

[0143]

The filler content of the rubber composition of the present embodiment is 5.0 ppm. or more and 150 m.ch. or less, preferably 20 m.h. or more and 100 m.ch. or less, and even more preferably 30 m.h. or more and 90 m.h. or less by 100 m.h. the rubber component containing the conjugated diene polymer of the present embodiment.

From the point of view of showing the effect of adding the filler, the content of the filler is 5.0 parts by mass or more, and from the point of view that the filler is sufficiently dispersed to achieve practically sufficient workability and mechanical strength of the rubber composition, its content is 150 ppm. or less.

[0144]

The silica-based inorganic filler is not particularly limited, any known filler may be used, particulate matter containing SiO ₂ or Si ₃ Al as a constituent block is preferred, and particulate matter containing SiO ₂ or Si ₃ Al as the main block is more preferred. component block. Here, the main component refers to a component contained in the silica-based inorganic filler in an amount of 50 mass% or more, preferably 70 mass% or more, and more preferably 80 mass% or more.

[0145]

Examples of the silica-based inorganic filler include, but are not limited to, silica, clay, talc, mica, diatomite, wollastonite, montmorillonite, zeolite, as well as inorganic fibrous materials such as glass fiber.

In addition, examples include a silica-based inorganic filler having a water-repellent surface, as well as a mixture of a silica-based inorganic filler and an inorganic filler excluding silica. Among them, in terms of strength and abrasion resistance, silica and glass fiber are preferable, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Of these, wet silica is preferred from the point of view that it has an excellent effect of improving fracture performance and balance in wet skid resistance.

[0146]

From the viewpoint of obtaining practically good abrasion resistance and degradation characteristics of the rubber composition, the nitrogen adsorption specific surface area obtained by the Brunauer-Emmett-Teller (BET) adsorption process of the silica-based inorganic filler is preferably 100 m ² /g or more and 300 m ² /g or less, and more preferably 170 m ² /g or more and 250 m ² /g or less. In addition, a silica-based inorganic filler having a relatively small specific surface area (for example, a specific surface area of 200 m ² /g or less) and a silica-based inorganic filler having a relatively large specific surface area (for example, 200 m ² /g or more), if necessary, can be used in combination.

If, in particular, a silica-based inorganic filler having a relatively large specific surface area (for example, 200 m ² /g or more), the conjugated diene-based polymer of the present embodiment has improved silica dispersibility, and is effective, in particular, to improve abrasion resistance and for a good balance of fracture characteristics and low hysteresis loss properties.

[0147]

The content of the silica-based inorganic filler in the rubber composition of the present embodiment is preferably 5.0 ppm. or more and 150 m.ch. or less, more preferably 20 m.h. or more and 100 m.ch. or less by 100 m.h. the rubber component containing the conjugated diene polymer of the present embodiment. In terms of showing the effect of adding the silica-based inorganic filler, the content of the silica-based inorganic filler is 5.0 ppm. or more, and from the point of view that the silica-based inorganic filler is sufficiently dispersed to achieve practically sufficient workability and mechanical strength of the rubber composition, its content is 150 ppm. or less.

[0148]

Examples of carbon blacks include, but are not limited to, carbon blacks of the SRF, FEF, HAF, ISAF, and SAF classes. Among them, a carbon black having a nitrogen adsorption specific surface area of 50 m ² /g or more and a dibutyl phthalate (DBP) oil absorption of 80 ml/100 g or less is preferable.

[0149]

The soot content is preferably 0.5 ppm. or more and 100 m.ch. or less, more preferably 3.0 m.h. or more and 100 m.ch. or less, and even more preferably 5.0 m.h. or more and 50 m.h. or less by 100 m.h. the rubber component containing the conjugated diene polymer of the present embodiment. From the point of view of exhibiting characteristics required for use as a tire and the like, such as dry grip performance and electrical conductivity, the soot content is preferably 0.5 ppm. or more, and from the point of view of dispersibility, its content is preferably 100 m.h. or less.

[0150]

Metal oxide refers to a solid particle containing a major constituent block component represented by the chemical formula MxOy (where M represents a metal atom and x and y each independently represent an integer from 1 to 6).

Examples of metal oxide include, but are not limited to, alumina, titanium oxide, magnesium oxide, and zinc oxide.

Examples of metal hydroxide include, but are not limited to, aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

[0151]

The rubber composition of the present embodiment may contain a silane binder.

The silane binder is preferably a compound which has the function of providing intimate interaction between the rubber component and the inorganic filler, has a group having an affinity or ability to bond with both of the rubber component and especially the silica-based inorganic filler, and contains a site in one molecule with a sulfur bond and a site with an alkoxysilyl or silanol group. Examples of such a compound include bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide and bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide.

[0152]

The content of the silane binder is preferably 0.1 ppm. or more and 30 m.h. or less, more preferably 0.5 m.h. or more and 20 m.ch. or less, and even more preferably 1.0 parts by weight or more and 15 m.h. or less by 100 m.h. filler. If the content of the silane coupling agent is within this range, the effect of adding the silane coupling agent may be more pronounced.

[0153]

The rubber composition of the present embodiment may contain a plasticizer from the viewpoint of improving workability.

As such a plasticizer, mineral oil or a liquid or a low molecular weight synthetic plasticizer is suitably used.

A mineral oil based plasticizer which is used for softening, filling and improving the machinability of rubber and is referred to as process oil or extender oil, is a mixture of aromatic ring, naphthenic ring and paraffin chain, and such a plasticizer in which the number of carbon atoms of the paraffin chain is 50 % or more of total carbon atoms is defined as a paraffin-based plasticizer, a plasticizer in which the number of carbon atoms of the naphthenic ring is 30% or more and 45% or less of the total carbon atoms is defined as a naphthene-based plasticizer, and a plasticizer , in which the number of aromatic carbon atoms exceeds 30% of the number of total carbon atoms, is defined as an aromatic compound plasticizer.

When the conjugated diene-based polymer of the present embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound, the plasticizer used preferably has a suitable aromatic content because such a plasticizer tends to suit the copolymer.

[0154]

The content of the plasticizer is preferably 0 ppm. or more and 100 m.ch. or less, more preferably 10 m.h. or more and 90 m.h. or less, and even more preferably 30 m.h. or more and 90 m.h. or less by 100 m.h. the rubber component containing the conjugated diene polymer of the present embodiment. If the content of the plasticizer is 100 m.h. or less by 100 m.h. of the rubber component, sweating is suppressed, and the tackiness of the surface of the rubber composition of the present embodiment is accordingly suppressed.

[0155]

Examples of the mixing method of the constituent materials of the rubber composition of the present embodiment, such as the rubber component containing the conjugated diene polymer of the present embodiment, the silica-based inorganic filler, carbon black or other filler, the silane binder, as well as additives such as a plasticizer, include includes, but is not limited to, a melt-kneading method using a conventional mixer, such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, or a multi-screw extruder, and a method in which the respective components are melted and mixed, followed by removal of the solvent by heating.

Among these methods, a melt-kneading method using a roll, a Banbury mixer, a kneader or an extruder is preferable in terms of productivity and high kneading ability. In addition, any of the methods in which the constituent materials of the rubber composition of the present embodiment are kneaded together or the method in which the materials are mixed separately and repeatedly are applicable.

[0156]

The rubber composition of the present embodiment may be a composition vulcanized with a vulcanizing agent. Examples of the curing agent include, but are not limited to, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds.

Sulfur compounds include sulfur chloride, sulfur dichloride, disulfide compounds and high molecular weight polysulfide compounds.

The content of the curing agent is preferably 0.01 ppm. or more and 20 m.ch. or less, and more preferably 0.1 m.h. or more and 15 m.ch. or less per 100 m.h. the rubber component containing the conjugated diene polymer of the present embodiment. As the vulcanization method, any known method can be used, and the vulcanization temperature is preferably 120°C or more and 200°C or less, and more preferably 140°C or more and 180°C or less.

[0157]

For vulcanization, if necessary, a vulcanization accelerator can be used.

As the vulcanization accelerator, any known material can be used, and examples include, but are not limited to, sulfenamide-based, guanidine-based, thiuram-based, aldehydeamine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based vulcanization accelerators. and based on dithiocarbamate.

In addition, examples of the vulcanization aid include, but are not limited to, zinc oxide and stearic acid.

The content of the vulcanization accelerator is preferably 0.01 ppm. or more and 20 m.ch. or less, and more preferably 0.1 m.h. or more and 15 m.ch. or less per 100 m.h. the rubber component containing the conjugated diene polymer of the present embodiment.

[0158]

The rubber composition of the present embodiment may contain, if the object of the present embodiment is not disturbed, various additives such as other plasticizer other than those described above, a filler, a heat-resistance stabilizer, an antistatic agent, a weather stabilizer, an antioxidant, a coloring agent, and a lubricant.

As another plasticizer, any of the known plasticizers can be used.

Specific examples of the other filler include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.

As each of the heat stabilizer, antistatic agent, weather stabilizer, antioxidant, dye, and lubricant, any of the known materials can be used.

[0159]

[Tire]

The rubber composition of the present embodiment is suitably used as a rubber composition for a tire. In other words, the tire of the present embodiment contains the rubber composition of the present embodiment.

[0160]

The tire rubber composition of the present embodiment is applicable to, but not limited to, various tires such as a fuel-efficient tire, an all-season tire, a high-tech tire, and a non-studded tire; as well as to various parts of the tire such as tread, carcass, sidewall and bead. In particular, since this tire rubber composition has an excellent balance between low hysteresis loss property and wet skid resistance in the form of a vulcanizate, as well as abrasion resistance, it is more suitably used as a tread of a fuel-efficient tire or a high-tech tire.

Examples

[0161]

The present embodiment will now be described in more detail with reference to specific examples and comparative examples, but the present embodiment is by no means limited to the following examples and comparative examples.

Various physical properties of the examples and comparative examples were measured by the following methods.

In the following examples and comparative examples, the conjugated diene-based polymer obtained after modification is referred to as "modified conjugated diene-based polymer". The polymer before modification is referred to as "non-modified conjugated diene polymer".

[0162]

(Physical property 1) Amount of bound styrene

One hundred (100) mg of the modified conjugated diene polymer used as a sample was dissolved in chloroform to a volume of 100 ml, and the resulting solution was used as a measurement sample. Based on the absorption value of the phenyl group of styrene at the absorption wavelength in the ultraviolet region (approximately 254 nm), the amount of bound styrene (wt.%) was measured on a 100 wt.% sample of the modified conjugated diene-based polymer (using a UV-2450 spectrophotometer » manufactured by Shimadzu Corporation).

[0163]

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

Fifty (50) mg of the modified conjugated diene polymer used as a sample was dissolved in 10 ml of carbon disulfide, and the resulting solution was used as a measurement sample.

The cuvette with the solution was used to measure the infrared spectrum in the range of 600-1000 cm ^-1 , and in accordance with the calculation formula of the Hampton method (RR Hampton, Analytical Chemistry 21, 923 (1949)) based on the optical density at a given wavelength, the microstructure of butadiene was obtained parts, namely the amount of 1,2-vinyl bond (mol.%) (using an infrared Fourier transform spectrophotometer "FT-IR230" manufactured by JASCO Corporation).

[0164]

(Physical property 3) Molecular weight

Measurement conditions 1: An unmodified conjugated diene based polymer or a modified conjugated diene based polymer used as a sample was measured to obtain a chromatogram using a GPC measurement device (trade name "HLC-8320GPC" manufactured by Tosoh Corporation) comprising three columns and using a polystyrene-based gel as a filler and an RI detector (trade name "HLC8020" manufactured by Tosoh Corporation), and based on the calibration curve obtained using standard polystyrene, the weight average molecular weight (Mw), the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn).

THF (tetrahydrofuran) containing 5 mmol/l triethylamine was used as the elution solvent. With respect to the columns used, a "TSKguardcolumn Super MP(HZ)-H" brand column manufactured by Tosoh Corporation was combined as a guard column in the previous step with a series of three "TSKgel Super Multipore HZ-H" brand columns manufactured by Tosoh Corporation.

Ten (10) mg of the measurement sample was dissolved in 10 ml of THF in order to obtain a measurement solution, and 10 μl of the measurement solution was injected into the GPC measurement device in order to perform measurement under the conditions of an oven temperature of 40°C and a volume flow rate THF 0.35 ml/min.

Among the various samples subjected to measurement under the above-described measurement conditions 1, a sample having a molecular weight distribution (Mw/Mn) of less than 1.6 was again subjected to measurement under measurement conditions 2 described below. As for the samples measured under measurement conditions 1, for which the molecular weight distribution was 1.6 or more, the results obtained by measurement under measurement conditions 1 are shown in Tables 1-3.

[0165]

Measurement conditions 2: An unmodified conjugated diene polymer or a modified conjugated diene polymer used as a sample was measured to obtain a chromatogram using a GPC measurement device including three columns and using a polystyrene-based gel as a filler, and based on a calibration curve obtained using a standard polystyrene, were obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

THF containing 5 mmol/l triethylamine was used as the elution solvent. The columns used were "TSKguardcolumn Super H-H" from Tosoh Corporation and "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" from Tosoh Corporation.

The RI detector (trade name "HLC8020" manufactured by Tosoh Corporation) was used under the condition of an oven temperature of 40°C and a THF flow rate of 0.6 ml/min. Ten (10) mg of the measurement sample was dissolved in 20 ml of THF to make the measurement solution, and 20 µl of the measurement solution was injected into the GPC measurement device to perform the measurement.

As for the sample measured under measurement conditions 1, for which the molecular weight distribution was less than 1.6, the results obtained by measurement under measurement conditions 2 are shown in Tables 1-3.

[0166]

(Physical property 4) Compression factor (g')

A modified conjugated diene-based polymer was used as a sample, and a GPC measurement device (trademark "GPCmax VE-2001" manufactured by Malvern Panalytical Ltd.) was used, including a series of three columns using a polystyrene-based gel as a filler. The measurement was performed by using three detectors, i.e. a light scattering detector, an RI detector, and a viscosity detector (trade name "TDA305" manufactured by Malvern Panalytical Ltd.) connected in the order shown in order to obtain, based on standard polystyrene, the absolute molecular weight from the results. obtained by the light scattering detector and the RI detector, and the intrinsic viscosity from the results obtained by the RI detector and the viscosity detector.

The straight chain polymer was used under the assumption of having an intrinsic viscosity [η] of -3.883 M ^0.771 and the compression factor (g') was calculated as the ratio of intrinsic viscosity to each molecular weight.

THF containing 5 mmol/l triethylamine was used as the elution solvent.

The coupled columns of the brands "TSKgel G4000HXL", "TSKgel G5000HXL" and "TSKgel G6000HXL" manufactured by Tosoh Corporation were used as columns.

Twenty (20) mg of the measurement sample was dissolved in 10 ml of THF in order to obtain a measurement solution, and 100 μl of the measurement solution was injected into the GPC measurement device in order to perform measurement under the conditions of an oven temperature of 40°C and a volume flow rate THF 1 ml/min.

[0167]

(Physical Property 5) Mooney Viscosity of Polymer

An unmodified conjugated diene based polymer or a modified conjugated diene based polymer was used as a sample for measuring Mooney viscosity by using a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) in accordance with JIS K6300 with rotor type L.

The measurement temperature was 110°C when an unmodified conjugated diene based polymer was used as a sample, and 100°C when a modified conjugated diene based polymer was used as a sample.

First, the sample was heated at the test temperature for 1 min, the rotor was rotated at 2 rpm, and the torque was measured 4 min later as Mooney viscosity (ML ₍₁₊₄₎ ).

[0168]

(Physical property 6) Glass transition temperature (Tg)

A modified conjugated diene based polymer was used as a sample, Mac Science's "DSC3200S" differential scanning calorimeter was used to record the DSC curve under a helium flow at a rate of 50 ml/min, with temperature increasing from -100°C at a rate of 20° C/min according to ISO 22768:2006, and the peak (inflection point) of the DSC differential curve thus obtained was defined as the glass transition temperature.

[0169]

(Physical property 7) Degree of modification

A modified conjugated diene polymer was used as a sample, and measurement was performed by applying a characteristic that the modified polymer base component is adsorbed on a GPC column using a silica gel as a filler.

The degree of modification was obtained by measuring the amount of adsorption on a silica column based on the difference between a chromatogram measured using a polystyrene column and a chromatogram measured using a silica column for a sample solution containing a sample and a low molecular weight polystyrene internal standard.

In particular, the measurement was performed as described below.

A sample that had a molecular weight distribution of 1.6 or more as a result of measurement (physical property 3) under measurement conditions 1 was measured under the following measurement conditions 3. A sample that had a molecular weight distribution of less than 1.6 as a result of measurement (physical property 3) under measurement conditions 1, measured under the following measurement conditions 4. The results are shown in Tables 1-3.

[0170]

Preparation of the sample solution: Ten (10) mg of the sample and 5 mg of standard polystyrene were dissolved in 20 ml of THF in order to obtain a sample solution.

Measurement conditions 3: GPC measurement conditions using a polystyrene column:

A device with the trademark "HLC-8320GPC" manufactured by Tosoh Corporation was used, THF containing 5 mmol/L triethylamine was used as the elution solvent, and 10 μl of the sample solution was injected into the device in order to obtain a chromatogram using an RI detector at under conditions of a column oven temperature of 40° C. and a THF flow rate of 0.35 ml/min.

As columns, a series of three columns of the trade name "TSKgel Super Multipore HZ-H" and a guard column of the trade mark "TSKguardcolumn SuperMP(HZ)-H" manufactured by Tosoh Corporation in the previous step were used.

[0171]

Measurement conditions 4: GPC measurement conditions using a polystyrene column:

The device of trade mark "HLC-8320GPC" manufactured by Tosoh Corporation was used, THF containing 5 mmol/l of triethylamine was used as the elution solvent, and 20 μl of the sample solution was injected into the device to perform the measurement.

The columns used were "TSKguardcolumn Super H-H" branded guard column manufactured by Tosoh Corporation and "TSKgel Super H5000", "TSKgel Super H6000" and "TSKgel Super H7000" branded columns manufactured by Tosoh Corporation were used. A chromatogram was obtained by performing a measurement using an RI detector (HLC8020, manufactured by Tosoh Corporation) under conditions of a column oven temperature of 40°C and a THF flow rate of 0.6 ml/min.

[0172]

Conditions for measuring GPC using a silica column:

The device with the trademark "HLC-8320GPC" manufactured by Tosoh Corporation was used, THF was used as the elution solvent, and 50 μl of the sample solution was injected into the device in order to obtain a chromatogram by using an RI detector under the conditions of a column oven temperature of 40°C and volumetric flow rate of THF 0.5 ml/min. A series of "Zorbax PSM-1000S", "PSM-300S" and "PSM-60S" brand columns and a "DIOL 4.6x12.5 mm 5 micron" brand guard column were used in the previous step.

[0173]

Method for calculating the degree of modification:

Assuming the total peak area of the chromatogram obtained using a polystyrene column is 100, the peak area of the sample is P1, the peak area of the standard polystyrene is P2, the total peak area of the chromatogram obtained using a silica column is 100, the peak area of the sample is P3 and the peak area of the standard polystyrene is P4, the degree of modification (%) was obtained according to the following expression:

Degree of Modification (%) = [1 - (P2 x P3)/(P1 x P4)] x 100

where P1+P2=P3+P4=100.

[0174]

(Physical property 8) Number of branches (Bn)

A modified conjugated diene-based polymer was used as a sample, and a GPC measurement device (trademark "GPCmax VE-2001" manufactured by Malvern Panalytical Ltd.) was used, including a series of three columns using a polystyrene-based gel as a filler. The measurement was performed using three detectors, i.e., a light scattering detector, an RI detector, and a viscosity detector (trade name "TDA305" manufactured by Malvern Panalytical Ltd.) connected in that order. Based on standard polystyrene, the absolute molecular weight was obtained from the results obtained using the light scattering detector and the RI detector, and the intrinsic viscosity was obtained from the results obtained using the RI detector and the viscosity detector.

The straight chain polymer was used under the assumption of having an intrinsic viscosity [η] of -3.883 M ^0.771 and the compression factor (g') was calculated as the ratio of intrinsic viscosity to each molecular weight.

Thereafter, the contraction factor (g') thus obtained was used to calculate the number of branches (Bn) based on the formula g' = 6 Bn/{(Bn+1)(Bn+2)}.

THF containing 5 mmol/l triethylamine was used as the elution solvent.

The coupled columns of the brands "TSKgel G4000HXL", "TSKgel G5000HXL" and "TSKgel G6000HXL" manufactured by Tosoh Corporation were used as columns.

Twenty (20) mg of the measurement sample was dissolved in 10 ml of THF in order to obtain a measurement solution, and 100 μl of the measurement solution was injected into the GPC measurement device in order to perform measurement under the conditions of an oven temperature of 40°C and a volume flow rate THF 1 ml/min.

[0175]

(Physical property 9) Molecular weight (absolute molecular weight) obtained by GPC light scattering measurement

A modified conjugated diene-based polymer was used as a sample, and a GPC light scattering apparatus including a series of three columns using a polystyrene-based gel as a filler was used to measure a chromatogram so as to obtain a weight average molecular weight (Mw-i ) (also referred to as "absolute molecular weight") based on the method of solution viscosity and light scattering.

As the elution solvent, a mixed solution of tetrahydrofuran and triethylamine (THF in TEA: prepared by mixing 5 ml of triethylamine and 1 l of tetrahydrofuran) was used.

As columns, a guard column of the brand "TSKguardcolumn HHR-H" manufactured by Tosoh Corporation and columns of the brands "TSKgel G6000HHR", "TSKgel G5000HHR" and "TSKgel G4000HHR" were used.

The GPC Light Scattering Device (trade name "Viscotek TDAmax" manufactured by Malvern Panalytical Ltd.) was used under oven temperature conditions of 40° C. and a THF flow rate of 1.0 ml/min.

Ten (10) mg of the measurement sample was dissolved in 20 ml of THF to make the measurement solution, and 200 µl of the measurement solution was injected into the GPC measurement device to perform the measurement.

[0176]

(Example 1) Modified conjugated diene polymer (sample 1)

Two pressure vessels in the fuel tank, each of which is a pressure vessel equipped with a stirrer, having an internal volume of 10 liters and a ratio (L/D) of internal height (L) to internal diameter (D) of 4.0, having an inlet at the bottom and outlet at the top, and equipped with a stirrer and a temperature control jacket, were connected to each other as polymerization reactors.

1,3-butadiene, styrene and n-hexane, from which the water had previously been removed, were mixed at a flow rate of 18.6 g/min, 10.0 g/min and 175.2 g/min, respectively. In a static mixer provided in the middle of the pipe for supplying the thus obtained mixed solution to the reactor, n-butyllithium for inactivating residual impurities was added and mixed in an amount of 0.103 mmol/min, and the resulting mixture was continuously fed to the bottom of the reactor. In addition, 2,2-bis(2-oxolanyl)propane, used as a polar material, and n-butyllithium, used as a polymerization initiator, were fed at a flow rate of 0.081 mmol/min and 0.143 mmol/min, respectively, to the lower part of the first reactor. , in which the materials were vigorously mixed with a stirrer, and the internal temperature of the reactor was maintained at 67°C.

The polymer solution thus obtained was continuously withdrawn from the top of the first reactor and continuously fed to the bottom of the second reactor in order to continue the reaction at 70° C., and the resulting solution was then fed to the static mixer from the top of the second reactor. When the polymerization was sufficiently stabilized, trimethoxy(4-vinylphenyl)silane (shown as "BS-1" in the table) used as a branching agent was added at a rate of 0.0190 mmol/min to the bottom of the second reactor. When the polymerization reaction and the branching reaction were stabilized, a small amount of the conjugated diene polymer solution was taken before adding the modifier, an antioxidant (BHT) was added to it in an amount of 0.2 g per 100 g of polymer, then the solvent was removed, and the viscosity was measured Mooney at 110°C and various molecular weights. Other physical properties are also shown in Table 1.

[0177]

Then, to the polymer solution flowing from the outlet of the reactor, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane (shown in the table as "A") as a modifier was continuously added at a rate of 0. 0360 mmol/min, and the resulting mixture was stirred using a static mixer to perform the modification reaction. Here, the time to add the modifier to the polymer solution flowing out of the reactor outlet was 4.8 minutes, the temperature was 68°C, and the difference between the temperature in the polymerization step and the temperature before adding the modifier was 2°C. To the polymer solution subjected to the modification reaction, an antioxidant (BHT) was continuously added in an amount of 0.2 g per 100 g of polymer at a rate of 0.055 g/min (n-hexane solution) to complete the modification reaction. Simultaneously with the antioxidant, an oil (JOMO Process NC 140 manufactured by JX Nippon Oil & Energy Corporation) was continuously added in an amount of 37.5 g per 100 g of polymer, and the resulting mixture was mixed using a static mixer. The solvent was removed by steam stripping, and thus a modified conjugated diene polymer was obtained (sample 1). The physical properties of sample 1 are shown in Table 1.

[0178]

(Example 2) Modified conjugated diene based polymer (sample 2)

The modified conjugated diene polymer (sample 2) was obtained in the same manner as in Example 1, except that the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza- 2-silacyclopentane to tris(3-trimethoxysilylpropyl)amine (shown as "B" in the table) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of sample 2 are shown in Table 1.

[0179]

(Example 3) Modified Conjugated Diene Polymer (Sample 3)

The modified conjugated diene polymer (sample 3) was obtained in the same manner as in Example 1, except that the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza- 2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (shown as "C" in the table) and that its addition amount was changed to 0.0190 mmol/min. The physical properties of sample 3 are shown in Table 1.

[0180]

(Example 4) Modified Conjugated Diene Polymer (Sample 4)

The modified conjugated diene based polymer (sample 4) was obtained in the same manner as in Example 1, except that the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza- 2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (shown as "C" in the table) and that its addition amount was changed to 0.0160 mmol/min. The physical properties of sample 4 are shown in Table 1.

[0181]

(Example 5) Modified Conjugated Diene Polymer (Sample 5)

The modified conjugated diene polymer (sample 5) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to dimethylmethoxy(4-vinylphenyl)silane (shown in the table as "BS-2"), and that its added amount was changed to 0.0350 mmol/min. The physical properties of sample 5 are shown in Table 1.

[0182]

(Example 6) Modified Conjugated Diene Polymer (Sample 6)

The modified conjugated diene based polymer (sample 6) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to dimethylmethoxy(4-vinylphenyl)silane (shown in the table as "BS-2"), its addition amount was changed to 0.0350 mmol/min, the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tris (3-trimethoxysilylpropyl)amine (shown as "B" in the table) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of sample 6 are shown in Table 1.

[0183]

(Example 7) Modified Conjugated Diene Polymer (Sample 7)

The modified conjugated diene polymer (sample 7) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to dimethylmethoxy(4-vinylphenyl)silane (shown in the table as "BS-2"), its addition amount was changed to 0.0350 mmol/min, the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tetrakis (3-trimethoxysilylpropyl)-1,3-propanediamine (shown as "C" in the table) and that its addition amount was changed to 0.0160 mmol/min. The physical properties of sample 7 are shown in Table 1.

[0184]

(Example 8) Modified Conjugated Diene Polymer (Sample 8)

The modified conjugated diene polymer (sample 8) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to 1,1-bis(4-dimethylmethoxysilyl )phenyl)ethylene (shown as "BS-3" in the table) and that its addition was changed to 0.0120 mmol/min. The physical properties of sample 8 are shown in Table 1.

[0185]

(Example 9) Modified Conjugated Diene Polymer (Sample 9)

The modified conjugated diene based polymer (sample 9) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to 1,1-bis(4-dimethylmethoxysilyl )phenyl)ethylene (shown in the table as "BS-3"), its addition amount was changed to 0.0120 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza -2-silacyclopentane to tris(3-trimethoxysilylpropyl)amine (shown as "B" in the table) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of sample 9 are shown in Table 1.

[0186]

(Example 10) Modified Conjugated Diene Polymer (Sample 10)

The modified conjugated diene polymer (sample 10) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to 1,1-bis(4-dimethylmethoxysilyl )phenyl)ethylene (shown in the table as "BS-3"), its addition amount was changed to 0.0120 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza -2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (shown as "C" in the table) and that its addition amount was changed to 0.0160 mmol/min. The physical properties of sample 10 are shown in Table 1.

[0187]

(Example 11) Modified Conjugated Diene Polymer (Sample 11)

The modified conjugated diene based polymer (sample 11) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to 1,1-bis(4-trimethoxysilylphenyl) )ethylene (shown as "BS-4" in the table) and that its addition was changed to 0.0210 mmol/min. The physical properties of sample 11 are shown in Table 2.

[0188]

(Example 12) Modified Conjugated Diene Polymer (Sample 12)

The modified conjugated diene polymer (sample 12) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to 1,1-bis(4-trimethoxysilylphenyl) )ethylene (shown in the table as "BS-4"), its addition amount was changed to 0.0210 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2 -silacyclopentane to tris(3-trimethoxysilylpropyl)amine (shown as "B" in the table) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of sample 12 are shown in Table 2.

[0189]

(Example 13) Modified Conjugated Diene Polymer (Sample 13)

The modified conjugated diene polymer (sample 13) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to 1,1-bis(4-trimethoxysilylphenyl) )ethylene (shown in the table as "BS-4"), its addition amount was changed to 0.0210 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2 -silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (shown as "C" in the table) and that its addition amount was changed to 0.0160 mmol/min. The physical properties of sample 13 are shown in Table 2.

[0190]

(Example 14) Modified Conjugated Diene Polymer (Sample 14)

The modified conjugated diene based polymer (sample 14) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to trichloro(4-vinylphenyl)silane (shown in the table as "BS-5"). The physical properties of sample 14 are shown in Table 2.

[0191]

(Example 15) Modified Conjugated Diene Polymer (Sample 15)

The modified conjugated diene polymer (sample 15) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to trichloro(4-vinylphenyl)silane (shown in the table as "BS-5"), the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tris(3-trimethoxysilylpropyl)amine (shown in the table as "B ”) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of sample 15 are shown in Table 2.

[0192]

(Example 16) Modified Conjugated Diene Polymer (Sample 16)

The modified conjugated diene polymer (sample 16) was obtained in the same manner as in Example 1, except that the branching agent was changed from trimethoxy(4-vinylphenyl)silane to trichloro(4-vinylphenyl)silane (shown in the table as "BS-5"), the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (shown in the table as "C"), and that its added amount was changed to 0.0160 mmol/min. The physical properties of sample 16 are shown in Table 2.

[0193]

(Example 17) Modified Conjugated Diene Polymer (Sample 17)

A modified conjugated diene based polymer (sample 17) was obtained in the same manner as in Example 1, except that the amount of trimethoxy(4-vinylphenyl)silane (shown as "BS-1" in the table) added to as branching agent was changed to 0.0100 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3 -propanediamine (shown in the table as "C"), and that its addition amount was changed to 0.0160 mmol/min. The physical properties of sample 17 are shown in Table 2.

[0194]

(Example 18) Modified Conjugated Diene Polymer (Sample 18)

A modified conjugated diene based polymer (sample 18) was obtained in the same manner as in Example 1, except that the amount of trimethoxy(4-vinylphenyl)silane (shown as "BS-1" in the table) added to as branching agent was changed to 0.0250 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3 -propanediamine (shown in the table as "C"), and that its addition amount was changed to 0.0160 mmol/min. The physical properties of sample 18 are shown in Table 2.

[0195]

(Example 19) Modified Conjugated Diene Polymer (Sample 19)

The modified conjugated diene polymer (sample 19) was obtained in the same manner as in Example 1, except that the amount of trimethoxy(4-vinylphenyl)silane (shown as "BS-1" in the table) added to as branching agent was changed to 0.0350 mmol/min, modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3 -propanediamine (shown in the table as "C"), and that its added amount was changed to 0.0160 mmol/min. The physical properties of Sample 19 are shown in Table 2.

[0196]

(Example 20) Conjugated Diene Polymer (Sample 20)

A conjugated diene based polymer (sample 20) was prepared in the same manner as in Example 1, except that the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2 -silacyclopentane to the binder tetraethoxysilane (shown as "D" in the table) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of sample 20 are shown in Table 2.

[0197]

(Comparative Example 1) Modified Conjugated Diene Resin (Sample 21)

Two pressure vessels, each of which was an agitated vessel reactor having an internal volume of 10 liters and a ratio (L/D) of internal height (L) to internal diameter (D) of 4.0, having an inlet at the bottom and an outlet at the top, and equipped with a stirrer and a temperature control jacket, were connected to each other as polymerization reactors.

1,3-butadiene, styrene and n-hexane, from which the water had previously been removed, were mixed at a flow rate of 18.6 g/min, 10.0 g/min and 175.2 g/min, respectively. In a static mixer provided in the middle of the pipe for supplying the thus obtained mixed solution to the reactor, n-butyllithium for inactivating residual impurities was added and mixed in an amount of 0.103 mmol/min, and the resulting mixture was continuously fed to the bottom of the reactor. In addition, 2,2-bis(2-oxolanyl)propane, used as a polar material, and n-butyllithium, used as a polymerization initiator, were fed at a flow rate of 0.081 mmol/min and 0.143 mmol/min, respectively, to the lower part of the first reactor. , in which the materials were vigorously mixed with a stirrer, and the internal temperature of the reactor was maintained at 67°C.

The polymer solution thus obtained was continuously withdrawn from the top of the first reactor and continuously fed to the bottom of the second reactor in order to continue the reaction at 70° C., and the resulting solution was then fed to the static mixer from the top of the second reactor. When the polymerization reaction was sufficiently stabilized, a small amount of polymer solution was taken before adding the modifier, an antioxidant (BHT) was added to it in an amount of 0.2 g per 100 g of polymer, then the solvent was removed, and Mooney viscosities were measured at 110 °C and various molecular weights. Other physical properties are also shown in Table 3.

[0198]

Then, to the polymer solution flowing from the outlet of the reactor, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane (shown in the table as "A") as a modifier was continuously added at a rate of 0. 0360 mmol/min, and the resulting mixture was stirred using a static mixer to perform the modification reaction. Here, the time to add the modifier to the polymer solution flowing out of the reactor outlet was 4.8 minutes, the temperature was 68°C, and the difference between the temperature in the polymerization step and the temperature before adding the modifier was 2°C. To the polymer solution subjected to the modification reaction, an antioxidant (BHT) was continuously added in an amount of 0.2 g per 100 g of polymer at a rate of 0.055 g/min (n-hexane solution) to complete the modification reaction. Simultaneously with the antioxidant, oil (JOMO Process NC 140 manufactured by JX Nippon Oil & Energy Corporation) was continuously added in an amount of 37.5 g per 100 g of polymer, and the resulting mixture was mixed using a static mixer. The solvent was removed by steam stripping, and thus a modified conjugated diene polymer was obtained (sample 21). The physical properties of sample 21 are shown in Table 3.

[0199]

(Comparative Example 2) Modified Conjugated Diene Resin (Sample 22)

The modified conjugated diene based polymer (Sample 22) was obtained in the same manner as in Comparative Example 1, except that the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza -2-silacyclopentane to tris(3-trimethoxysilylpropyl)amine (shown as "B" in the table) and that its addition amount was changed to 0.0250 mmol/min. The physical properties of Sample 22 are shown in Table 3.

[0200]

(Comparative Example 3) Diene-based branched modified polymer (Sample 23)

A modified conjugated diene based polymer (Sample 23) was obtained in the same manner as in Comparative Example 1, except that the modifier was changed from 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza -2-silacyclopentane to tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine (shown as "C" in the table) and that its addition amount was changed to 0.0190 mmol/min. The physical properties of Sample 23 are shown in Table 3.

[0201]

(Comparative Example 4) Diene-based branched modified polymer (Sample 24)

The modified conjugated diene polymer (Sample 24) was obtained in the same manner as in Comparative Example 1, except that the amount of 2,2-bis(2-oxolanyl)propane added as a polar material was changed by 0.105 mmol/min, the amount of n-butyllithium added as a polymerization initiator was changed to 0.188 mmol/min, the amount of trimethoxy(4-vinylphenyl)silane (shown as "BS-1" in the table) added as a branching agent , was changed to 0.0350 mmol/min, and the amount of 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane added as modifier was changed to 0.0510 mmol/min. The physical properties of Sample 24 are shown in Table 3.

[0202]

(Comparative Example 5) Modified Conjugated Diene Resin (Sample 25)

One pressure vessel, which was an agitated vessel reactor having an internal volume of 0.5 L and a ratio (L/D) of internal height (L) to internal diameter (D) of 4.0, having an inlet at the bottom and an outlet at the top, provided with a stirrer and temperature control jacket, and two pressure vessels, each of which was a stirred tank reactor having an internal volume of 10 liters and a ratio (L/D) of internal height (L) to internal diameter (D) 4.0, having an inlet at the bottom and an outlet at the top, equipped with a stirrer and a temperature control jacket, were connected to each other, namely, a total of three reactors were connected as polymerization reactors.

n-hexane, from which water had previously been removed, 2,2-bis(2-oxolanyl)propane used as a polar material, n-butyllithium used as a polymerization initiator, and n-butyllithium to inactivate residual impurities were added at a cost 175.2 g/min, 0.081 mmol/min, 0.143 mmol/min, and 0.103 mmol/min, respectively, and trimethoxy(4-vinylphenyl)silane (shown as "BS-1" in the table) were added as branching agent at a rate of 0 .0190 mmol/min. The resulting mixture was vigorously stirred with a stirrer and the internal temperature of the reactor was maintained at 67° C. to create a polymer block component.

The polymer solution thus obtained was continuously taken from the top of the first reactor and continuously fed to the bottom of the second reactor, and 1,3-butadiene and styrene, from which water had previously been removed, were fed to the bottom of the second reactor at a flow rate of 18.6 g/ min and 10.0 g/min, respectively, and mixed.

The reaction was continued at 70° C. and the resulting polymer solution was continuously withdrawn from the top of the second reactor, continuously fed to the bottom of the third reactor, and further fed to the static mixer from the top of the third reactor. The mixed solution thus obtained was fed into a static mixer provided in the middle of the pipe to be fed to the inlet of the third reactor. When the polymerization reaction was sufficiently stabilized, a small amount of polymer solution was taken before adding the modifier, an antioxidant (BHT) was added to it in an amount of 0.2 g per 100 g of polymer, then the solvent was removed, and Mooney viscosities were measured at 110 °C and various molecular weights. Other physical properties are also shown in Table 3.

[0203]

Then, to the polymer solution flowing from the outlet of the reactor, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane (shown in the table as "A") as a modifier was continuously added at a rate of 0. 0360 mmol/min, and the resulting mixture was stirred using a static mixer to perform the modification reaction. Here, the time to add the modifier to the polymer solution flowing out of the reactor outlet was 4.8 minutes, the temperature was 68°C, and the difference between the temperature in the polymerization step and the temperature before adding the modifier was 2°C. To the polymer solution subjected to the modification reaction, an antioxidant (BHT) was continuously added in an amount of 0.2 g per 100 g of polymer at a rate of 0.055 g/min (n-hexane solution) to complete the modification reaction. Simultaneously with the antioxidant, an oil (JOMO Process NC 140 manufactured by JX Nippon Oil & Energy Corporation) was continuously added in an amount of 37.5 g per 100 g of polymer, and the resulting mixture was mixed using a static mixer. The solvent was removed by steam stripping, and thus a modified conjugated diene polymer was obtained (sample 25). The physical properties of Sample 25 are shown in Table 3.

[0204]

[Table 1]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Modified Conjugated Diene-Based Polymer (Sample No.) one 2 3 four 5 6 7 eight 9 ten Polymerization conditions Butadiene (g/min) 18.6 18.6 18.6 18.6 18.6 18.6 18.6 18.6 18.6 18.6 Styrene (g/min) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 n-hexane (g/min) 175.2 175.2 175.2 175.2 175.2 175.2 175.2 175.2 175.2 175.2 Polymerization temperature (ºC) 70 70 70 70 70 70 70 70 70 70 n-butyl lithium for processing (mmol/min) 0.103 0.103 0.103 0.103 0.103 0.103 0.103 0.103 0.103 0.103 n-butyllithium polymerization initiator (mmol/min) 0.143 0.143 0.143 0.143 0.143 0.143 0.143 0.143 0.143 0.143 Amount of added polar material (mmol/min) 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 Branch Agent Type of BS-1 BS-1 BS-1 BS-1 BS-2 BS-2 BS-2 BS-3 BS-3 BS-3 Added quantity (mmol/min) 0.0190 0.0190 0.0190 0.0190 0.0350 0.0350 0.0350 0.0120 0.0120 0.0120 Modifier Type of A B C C A B C A B C Added quantity (mmol/min) 0.0360 0.0250 0.0190 0.0160 0.0360 0.0250 0.0160 0.0360 0.0250 0.0160 Physical Properties Conjugated diene based polymer (Physical property 3) Weight average molecular weight (10 ⁴ g/mol) 63.9 63.9 63.9 63.9 60.3 60.3 60.3 74.5 74.5 74.5 (Physical property 3) Number average molecular weight (10 ⁴ g/mol) 33.1 33.1 33.1 33.1 32.2 32.2 32.2 37.8 37.8 37.8 (Physical Property 4) Mooney Viscosity (110°C) 92.1 92.1 92.1 92.1 88.2 88.2 88.2 99.1 99.1 99.1 (Physical property 3) Mw/Mn 1.93 1.93 1.93 1.93 1.87 1.87 1.87 1.97 1.97 1.97 Modified polymer based on conjugated diene (Physical property 1) Amount of bound styrene (wt%) 35 35 35 35 35 35 35 35 35 35 (Physical property 2) Amount of bound vinyl (amount of 1,2-bond) (mol.%) 40 40 40 40 40 40 40 40 40 40 (Physical property 3) Weight average molecular weight (10 ⁴ g/mol) 92.0 96.0 105.3 106.0 86.8 90.6 99.4 115.0 121.0 135.0 (Physical property 3) Number average molecular weight (10 ⁴ g/mol) 46.7 48.7 53.4 54.6 43.8 46.5 51.5 57.2 62.4 69.6 (Physical property 3) Mw/Mn 1.97 1.97 1.97 1.94 1.98 1.95 1.93 2.01 1.94 1.94 (Physical property 4) Compression factor (g') 0.52 0.40 0.32 0.26 0.53 0.45 0.37 0.28 0.21 0.18 (Physical Property 5) Polymer Mooney Viscosity (100°C) 83 83 83 82 79 84 82 81 84 82 (Physical property 6) Glass transition temperature (ºC) -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 (Physical property 7) Degree of modification (%) 88 86 86 82 85 84 81 82 84 85 (Physical property 8) Number of branches Bn per molecule 8.7 12.0 15.8 20.0 8.0 10.0 13.0 18.0 26.0 30.0 (Physical property 9) Absolute molecular weight (Mw-i) (10 ⁴ Daltons) 144 170 186 281 136 160 176 160 203 334.8

[0205]

[Table 2]

Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Modified Conjugated Diene-Based Polymer (Sample No.) eleven 12 13 fourteen fifteen 16 17 eighteen 19 twenty Polymerization conditions Butadiene (g/min) 18.6 18.6 18.6 18.6 18.6 18.6 18.6 18.6 18.6 18.6 Styrene (g/min) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 n-hexane (g/min) 175.2 175.2 175.2 175.2 175.2 175.2 175.2 175.2 175.2 175.2 Polymerization temperature (ºC) 70 70 70 70 70 70 70 70 70 70 n-butyl lithium for processing (mmol/min) 0.103 0.103 0.103 0.103 0.103 0.103 0.103 0.103 0.103 0.103 n-butyllithium polymerization initiator (mmol/min) 0.143 0.143 0.143 0.143 0.143 0.143 0.143 0.143 0.143 0.143 Amount of added polar material (mmol/min) 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 Branch Agent Type of BS-4 BS-4 BS-4 BS-5 BS-5 BS-5 BS-1 BS-1 BS-1 BS-1 Added quantity (mmol/min) 0.0210 0.0210 0.0210 0.0190 0.0190 0.0190 0.0100 0.0250 0.0350 0.0190 Modifier Type of A B C A B C C C C D Added quantity (mmol/min) 0.0360 0.0250 0.0160 0.0360 0.0250 0.0190 0.0160 0.0160 0.0160 0.0250 Physical properties Conjugated diene based polymer (Physical property 3) Weight average molecular weight (10 ⁴ g/mol) 61.5 61.5 61.5 63.9 63.9 63.9 55.9 78.6 89.3 63.9 (Physical property 3) Number average molecular weight (10 ⁴ g/mol) 31.1 31.1 31.1 33.1 33.1 33.1 28.5 40.1 45.1 33.1 (Physical Property 4) Mooney Viscosity (110°C) 90.6 90.6 90.6 92.1 92.1 92.1 88.1 98.1 105.3 92.1 (Physical property 3) Mw/Mn 1.98 1.98 1.98 1.93 1.93 1.93 1.96 1.96 1.98 1.93 Modified polymer based on conjugated diene (Physical property 1) Amount of bound styrene (wt%) 35 35 35 35 35 35 35 35 35 35 (Physical property 2) Amount of bound vinyl (amount of 1,2-bond) (mol.%) 40 40 40 40 40 40 40 40 40 40 (Physical property 3) Weight average molecular weight (10 ⁴ g/mol) 91.0 94.0 102.3 92.0 96.0 105.3 98.1 117.0 125.0 95.8 (Physical property 3) Number average molecular weight (10 ⁴ g/mol) 46.0 48.2 51.9 46.7 48.7 53.4 50.6 59.7 62.2 48.4 (Physical property 3) Mw/Mn 1.98 1.95 1.97 1.97 1.97 1.97 1.94 1.96 2.01 1.98 (Physical property 4) Compression factor (g') 0.51 0.41 0.35 0.52 0.40 0.32 0.38 0.21 0.18 0.40 (Physical Property 5) Polymer Mooney Viscosity (100°C) 82 83 84 83 83 83 87 90 92 80 (Physical property 6) Glass transition temperature (ºC) -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 (Physical property 7) Degree of modification (%) 82 84 62 88 86 86 92 75 68 0 (Physical property 8) Number of branches Bn per molecule 8.5 11.5 14.2 8.7 12.0 15.8 12.5 25.3 30.1 12.0 (Physical property 9) Absolute molecular weight (Mw-i) (10 ⁴ Daltons) 135 165 184 144 170 186 245 320 360 158

[0206]

[Table 3]

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Modified Conjugated Diene-Based Polymer (Sample No.) 21 22 23 24 25 Polymerization conditions Butadiene (g/min) 18.6 18.6 18.6 18.6 18.6 Styrene (g/min) 10.0 10.0 10.0 10.0 10.0 n-hexane (g/min) 175.2 175.2 175.2 175.2 175.2 Polymerization temperature (ºC) 70 70 70 70 70 n-butyllithium for processing (mmol/min) 0.103 0.103 0.103 0.103 0.103 n-butyllithium polymerization initiator (mmol/min) 0.143 0.143 0.143 0.188 0.143 Amount of added polar material (mmol/min) 0.081 0.081 0.081 0.105 0.081 Branch Agent Type of - - - BS-1 BS-1 Added quantity (mmol/min) - - - 0.0350 0.0190 Modifier Type of A B C A A Added quantity (mmol/min) 0.0360 0.0250 0.0190 0.0510 0.0360 Physical properties Conjugated diene based polymer (Physical property 3) Weight average molecular weight (10 ⁴ g/mol) 48.9 48.9 48.9 18.9 49.0 (Physical property 3) Number average molecular weight (10 ⁴ g/mol) 27.9 27.9 27.9 9.6 28.0 (Physical Property 4) Mooney Viscosity (110°C) 72.5 72.5 72.5 25 72.6 (Physical property 3) Mw/Mn 1.75 1.75 1.75 1.97 1.75 Modified polymer based on conjugated diene (Physical property 1) Amount of bound styrene (wt%) 35 35 35 35 35 (Physical property 2) Amount of bonded vinyl (amount of 1,2-bond) (mol.%) 40 40 40 40 40 (Physical property 3) Weight average molecular weight (10 ⁴ g/mol) 82.1 94.3 117.4 27.2 82.1 (Physical property 3) Number average molecular weight (10 ⁴ g/mol) 40.8 47.9 53.4 13.5 40.8 (Physical property 3) Mw/Mn 2.01 1.97 1.98 2.01 2.01 (Physical property 4) Compression factor (g') 0.91 0.74 0.56 0.52 0.91 (Physical Property 5) Polymer Mooney Viscosity (100°C) 75 83 96 40 75 (Physical property 6) Glass transition temperature (ºC) -23 -23 -23 -23 -23 (Physical property 7) Degree of modification (%) 83 86 80 82 83 (Physical property 8) Number of branches Bn per molecule 2.9 4.6 7.4 8.4 2.9 (Physical property 9) Absolute molecular weight (Mw-i) (10 ⁴ Daltons) 96 97 142 38 96

[0207]

(Examples 21-40 and Comparative Examples 6-10)

Samples 1-25 shown in Tables 1-3 were used respectively as raw rubbers to obtain rubber compositions containing these raw rubbers, in accordance with the following composition:

Conjugated diene polymer or modified conjugated diene polymer (each of Samples 1-25): 100 ppm (excluding oil)

Silica 1 (trade name "Ultrasil 7000GR" manufactured by Evonik Degussa, nitrogen adsorption specific surface area: 170 m ² /g): 50.0 m.h.

Silica 2 (trademark "Zeosil Premium 200MP" manufactured by Rhodia, nitrogen adsorption specific surface area: 220 m ² /g): 25.0 m.h.

Carbon black (trade name "Seast KH (N339)", manufactured by Tokai Carbon Co., Ltd.): 5.0 ppm

Silane binder: (trademark "Si75", manufactured by Evonik Degussa, bis(triethoxysilylpropyl) disulfide): 6.0 ppm

S-RAE oil (trade name "Process NC140", manufactured by JX Nippon Oil & Energy Corporation): 37.5 ppm

Zinc oxide: 2.5 ppm

Stearic acid: 1.0 m.h.

Antioxidant (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine): 2.0 m.h.

Sulfur: 2.2 ppm

Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide): 1.7 m.h.

Vulcanization accelerator 2 (diphenylguanidine): 2.0 m.h.

Total: 239.4 m.h.

[0208]

The above materials were kneaded in the following way to obtain a rubber composition. A closed kneader (having an internal volume of 0.3 L) equipped with a temperature controller was used for mixing as the first stage of mixing raw rubber (each of samples 1-25), fillers (silica 1, silica 2 and carbon black), silane binder, process oil, zinc oxide and stearic acid under conditions of 65% filling and a rotor speed of 30-50 rpm. At the same time, the temperature of the closed kneader was controlled so as to obtain each rubber composition (compound) at an exit temperature of 155-160°C.

[0209]

Then, after the compound described above was cooled to room temperature, an antioxidant was added thereto as a second mixing step, and the resulting mixture was kneaded again to improve the dispersibility of the silica. In this case, the outlet temperature of the compound was also maintained in the range of 155-160°C by controlling the temperature of the mixer. After cooling, sulfur and vulcanization accelerators 1 and 2 were added as the third mixing step, and the resulting mixture was kneaded with an open roller at a temperature of 70°C. Thereafter, the resulting mixture was molded and vulcanized at 160° C. for 20 minutes with a vulcanizing press. Evaluated rubber compositions before vulcanization and rubber compositions after vulcanization. In particular, the evaluation was performed as described below. The results are shown in Tables 4-6.

[0210]

(Score 1) Compound Mooney Viscosity

Each compound obtained after the second mixing step and before the third mixing step was used as a sample for measuring viscosity using a Mooney viscometer in accordance with JIS K6300-1 after heating the compound at 130°C for 1 min and after rotating the rotor for 4 min at 2 rpm. The viscosity thus obtained was used as an index obtained under the condition that the result of Comparative Example 6 was 100. A smaller index indicates better workability.

[0211]

(Score 2) Viscoelasticity parameter

ARES Viscoelasticity Testing Machine manufactured by Rheometric Scientific, Inc. was used to measure the viscoelasticity parameter in torsion mode. Each measurement value was used as an index obtained under the condition that the result obtained by the rubber composition of Comparative Example 6 was 100. The tan δ value measured at 0°C, a frequency of 10 Hz, and a deformation of 1% was used as an adhesion performance index wet tires. A higher index indicates better wet grip performance. In addition, the tan δ value measured at 50° C., 10 Hz, and 3% strain was used as the fuel efficiency index. A lower index indicates higher fuel efficiency.

[0212]

(Grade 3) Tensile strength and elongation

Tensile strength and elongation were measured in accordance with the tensile test method of JIS K6251, and were used as indices, provided that the results of Comparative Example 6 were 100. A larger index indicates better tensile strength and elongation.

[0213]

(Grade 4) Abrasion resistance

Acron abrasion test machine (manufactured by Yasuda Seiki Seisakusho, Ltd.) was used to measure the degree of abrasion per 1000 revolutions under a load of 44.4 N in accordance with JIS K6264-2, and were used as indices provided that the result Comparative Example 6 was 100. A larger index indicates better abrasion resistance.

[0214]

[Table 4]

Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Modified Diene-Based Polymer (Sample No.) one 2 3 four 5 6 7 eight 9 ten (Physical Property 5) Mooney Viscosity of Modified Diene-Based Polymer (100°C) 83 83 83 82 79 84 82 81 84 82 (Grade 1) Compound Mooney Viscosity (130°C) Index 83 85 80 78 84 85 78 78 78 78 Physical properties of the vulcanizate (Rating 2) tanδ value at 50°C (strain 3%) Index 80 75 70 73 82 83 73 73 75 77 (Rating 2) tanδ value at 0°C (strain 1%) Index 120 125 130 128 115 120 128 124 120 121 (Grade 3) Tensile strength Index 110 125 130 140 109 125 130 143 150 155 (Score 3) Tensile elongation Index 120 130 140 145 122 130 145 150 151 151 (Grade 4) Abrasion resistance Index 125 130 140 150 123 130 145 160 162 165

[0215]

[Table 5]

Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Modified Diene-Based Polymer (Sample No.) eleven 12 13 fourteen fifteen 16 17 eighteen 19 twenty (Physical Property 5) Mooney Viscosity of Modified Diene-Based Polymer (100°C) 82 83 84 83 83 83 87 90 92 90 (Grade 1) Compound Mooney Viscosity (130°C) Index 89 87 82 86 85 80 82 72 68 100 Physical properties of the vulcanizate (Rating 2) tanδ value at 50°C (strain 3%) Index 85 80 75 80 75 70 70 83 85 83 (Rating 2) tanδ value at 0°C (strain 1%) Index 115 120 125 120 125 130 130 115 110 120 (Grade 3) Tensile strength Index 110 120 125 110 125 130 110 150 160 120 (Score 3) Tensile elongation Index 119 130 140 120 130 140 120 149 166 107 (Grade 4) Abrasion resistance Index 124 130 140 125 130 140 130 155 160 120

[0216]

[Table 6]

Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 10 Comparative Example 11 Modified Diene-Based Polymer (Sample No.) 21 22 23 24 25 (Physical Property 5) Mooney Viscosity of Modified Diene-Based Polymer (100°C) 75 83 96 96 90 (Grade 1) Compound Mooney Viscosity (130°C) Index 100 98 94 40 101 Physical properties of the vulcanizate (Rating 2) tanδ value at 50°C (strain 3%) Index 100 90 85 70 102 (Rating 2) tanδ value at 0°C (strain 1%) Index 100 103 109 109 100 (Grade 3) Tensile strength Index 100 95 90 78 100 (Score 3) Tensile elongation Index 100 98 92 77 105 (Grade 4) Abrasion resistance Index 100 110 115 76 105

[0217]

As shown in Tables 4-6, Examples 21-40 were confirmed to have an excellent balance between wet slip resistance and low hysteresis loss property in the form of a vulcanizate, as well as excellent abrasion resistance compared to Comparative Examples 6-11.

It has also been confirmed that they have such a low Mooney viscosity in the form of a vulcanizate that good workability can be ensured.

It has also been confirmed that they have practically sufficient fracture strength in the form of a vulcanizate.

[0218]

This application is based on an earlier Japanese patent application (Japanese Patent Application No. 2018-188604) filed with the Japan Patent Office on October 3, 2018, the entire content of which is incorporated herein by reference.

INDUSTRIAL APPLICABILITY

[0219]

The conjugated diene-based polymer of the present invention can be used industrially as a material and the like. tire treads, vehicle interior/exterior materials, damping rubber products, belts, shoes, foam bodies and various industrial products.

Claims (24)

1. A conjugated diene-based polymer having an absolute molecular weight measured by gel permeation chromatography (GPC) light scattering determination with a viscosity detector of 100×10 ⁴ or more and 5000×10 ⁴ or less, and having a number of branches (Bn) measured by GPC light scattering detection with a viscosity detector equal to 8 or more, where the upper limit of Bn is 84 or less. 2. The conjugated diene based polymer according to claim 1, having a degree of modification of 60% by weight or more. 3. A conjugated diene based polymer according to claim 1 or 2, which has a star-shaped polymer structure having 3 or more branches, in which at least one branched star chain contains a moiety derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, and a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group further contains a branched main chain structure. 4. A polymer based on a conjugated diene according to any one of paragraphs. 1-3, in which the part obtained from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is a monomer unit based on the compound represented by the following formula (1) or (2), and contains a branching point of a polymer chain containing a monomer unit based on the compound, represented by formula (1) or (2), and at least one end of the conjugated diene polymer is bonded using a binder:

where in the formula (1) R ¹ represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part; each of R ² and R ³ independently represents an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and may have a branched structure in its part; each of R ¹ -R ³ if they are present in the plural, is respectively independent; X ¹ represents an independent halogen atom; m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3; in the formula (2), each of R ² to R ⁵ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in its part, and each of R ² - R ⁵ if they are present in the plural, is respectively independent; X ² and X ³ represent an independent halogen atom; m represents an integer from 0 to 2, n represents an integer from 0 to 3, l represents an integer from 0 to 3, and (m+n+l) is 3; and a represents an integer from 0 to 2, b represents an integer from 0 to 3, c represents an integer from 0 to 3, and (a+b+c) is 3. 5. The conjugated diene-based polymer according to claim 4, containing a monomer unit based on the compound represented by formula (1), in which R ¹ is a hydrogen atom and m is 0. 6. The conjugated diene-based polymer according to claim 4, containing a monomer unit based on the compound represented by formula (2), in which m is 0 and b is 0. 7. The conjugated diene-based polymer according to claim 4, containing a monomer unit based on the compound represented by formula (1), in which R ¹ is a hydrogen atom, and m is 0 and l is 0. 8. The conjugated diene-based polymer according to claim 4, containing a monomer unit based on the compound represented by formula (2), in which m is 0, l is 0, a is 0, and b is 0. 9. The conjugated diene-based polymer according to claim 4, containing a monomer unit based on the compound represented by formula (1), in which R ¹ is a hydrogen atom, l is 0 and n is 3.