JP5844575B2 - Method for producing modified conjugated diene polymer, modified conjugated diene polymer, modified conjugated diene polymer composition, and tire - Google Patents

Description

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

  In recent years, environmental considerations, such as the suppression of carbon dioxide emissions, have become social demands, and the demand for lower fuel consumption for automobiles has increased. Under such circumstances, development of a material having low rolling resistance is demanded as a material for automobile tires, particularly tire treads that are in contact with the ground.

Conventionally, carbon black, silica, and the like have been used as reinforcing fillers for tire treads.
When silica is used as the reinforcing filler, there is an advantage that low hysteresis loss and wet skid resistance can be improved.
On the other hand, since silica with a hydrophilic surface has a low affinity with a conjugated diene rubber and has a disadvantage of poor dispersibility compared with carbon black, with respect to carbon black with a hydrophobic surface, In order to improve dispersibility or to provide a bond between silica and rubber, it is necessary to contain a silane coupling agent separately.
In view of such problems related to silica, the dispersibility of silica in a conjugated diene rubber material can be improved by introducing functional groups having affinity and reactivity with silica at the end of rubber molecules having high mobility. Attempts have been made to improve the hysteresis loss and further to reduce the hysteresis loss by sealing the rubber molecule end with a silica particle bond.

For example, a modified diene rubber obtained by reacting a modifier having a glycidylamino group at the end of a diene polymer (see, for example, Patent Document 1) and glycidoxyalkoxysilane are reacted at the end of a diene polymer. Modified diene rubbers obtained (for example, see Patent Document 2), and further modified diene rubbers obtained by reacting aminosilane-containing alkoxysilanes with diene polymer terminals (for example, Patent Documents 3 and 4). And a composition combining these with silica has been proposed.
In addition, the diene rubber is polymerized using a polyfunctional anionic polymerization initiator, and then modified with a modifying agent such as a glycidylamino group to increase the number of functionalized polymer ends, thereby diene rubber. A technique for improving the performance of a composition composed of silica and silica, that is, silica dispersibility and reducing hysteresis loss (see, for example, Patent Document 5) has also been proposed.

International Publication No. 01/23467 Pamphlet Japanese Patent Application Laid-Open No. 07-233217 JP 2001-158834 A JP 2003-171418 A JP 2006-306962 A

  However, in recent years, with the further increase in demand for lower fuel consumption, development of rubber compositions excellent in various performances such as reduction of hysteresis loss has been demanded.

  Therefore, in the present invention, when a vulcanizate containing a silica-based inorganic filler is used, it has an excellent balance between low hysteresis loss and safety-related characteristics such as wet skid resistance and low temperature characteristics, and has practically sufficient resistance. A modified conjugated diene polymer composition having abrasion and fracture strength and satisfying good processability, a tire containing the modified conjugated diene polymer composition, and the modified conjugated diene polymer composition It is an object of the present invention to provide a modified conjugated diene polymer constituting a product and a production method thereof.

As a result of intensive studies to solve the problems of the prior art, the present inventors have polymerized using a specific polyfunctional anionic polymerization initiator, and a compound having a specific functional group at a polymerization active terminal. The present inventors have found that a modified conjugated diene polymer composition containing a modified conjugated diene polymer obtained by modification can solve the above-mentioned problems, and completed the present invention.
That is, the present invention is as follows.

[1]
Polymerizing a conjugated diene compound or a conjugated diene compound with a polyfunctional anionic polymerization initiator having a molecular weight distribution measured using gel permeation chromatography (GPC) in the range of 1.2 to 3.5 Obtaining a conjugated diene polymer obtained by copolymerizing with an aromatic vinyl compound;
At the polymerization active terminal of the conjugated diene polymer,
(I) a step in which the total number of alkoxy groups bonded to the silyl group is 4 or more and the modifier (A) having one or more nitrogen atoms is reacted;
(II) a step of reacting a modifying agent (B) in which the total number of alkoxy groups bonded to the silyl group is 2 or 3, and having one or more nitrogen atoms;
Having
A method for producing a modified conjugated diene polymer.
[2]
The polyfunctional anionic polymerization initiator is prepared in a hydrocarbon solvent with a polyvinyl aromatic compound and an organic lithium compound at a molar ratio of polyvinyl aromatic compound / organic lithium compound in the range of 0.01 to 1.0. The method for producing a modified conjugated diene polymer according to [1], which is a polyfunctional anionic polymerization initiator.
[3]
The total number of alkoxy groups bonded to the silyl group is 4 or more, and the modifier (A) having one or more nitrogen atoms is a compound represented by the following general formula (1) or general formula (2). A method for producing a modified conjugated diene polymer according to [1] or [2].

In the general formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group, and R ⁸ and R ⁹ each represents an alkylene group having 1 to 20 carbon atoms. M is an integer of 1 or 2, and n is an integer of 2 or 3. In the compound represented by the general formula (1), the total number of alkoxy groups having 1 to 20 carbon atoms is 4 or more.

In the general formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group, and R ⁸ and R ⁹ are each an alkylene group having 1 to 20 carbon atoms. And when a plurality of R ⁸ , R ⁹ and A ¹ are present, they may be the same or different. m and n are each an integer of 0 to 3.
p is an integer of 0 to 20, and when p is 2 or more, the plurality of repeating units represented by (R ⁹ -A ¹ -R ⁸ ) may be different from each other. In the compound represented by the general formula (2), the total number of alkoxy groups having 1 to 20 carbon atoms is 4 or more. A ¹ is a group represented by any one of the following general formulas (a), (b), and (c).

In the general formula (a), R ¹⁰ and R ¹¹ are each an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.

In the general formula (b), R ⁷ is an alkyl or aryl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen, and triorgano-substituted silyl. Any one selected from the group consisting of groups.

In the general formula (c), R ¹⁰ is an alkylene group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are an alkyl group or aryl group having 1 to 20 carbon atoms. r is an integer of 0-3.

[4]
The total number of alkoxy groups bonded to the silyl group is 2 or 3, and the modifier (B) having one or more nitrogen atoms is represented by the following general formula (3), general formula (4), and general formula (5). ), The general formula (6), the general formula (7), and the modification according to any one of [3], which is any one selected from the group consisting of compounds represented by the general formula (8) A method for producing a conjugated diene polymer.

In the general formula ^{(3), R 1, R} 2 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ^8, R ⁹ represents an alkylene group having 1 to 20 carbon atoms , R ¹² , R ¹³ , and R ¹⁴ contain Si, O, or N, and may be substituted with an organic group having no active hydrogen.
20 hydrocarbon groups. i is an integer of 2 or 3 .

In the general formula ^{(4), R 1, R} 2 are each independently an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁹ is an alkylene group having 1 to 20 carbon atoms, R ^10, R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms and has a ring structure of 5 or more members with two adjacent N atoms, and R ¹⁵ has no hydrocarbon group having 1 to 20 carbon atoms and active hydrogen. It is a C1-C20 hydrocarbon group substituted by the hetero atom, or a 3 organic substituted silyl group, and m is an integer of 2 or 3.

In Formula ^{(5), R 1, R} 2 are each independently an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁹ is an alkylene group having 1 to 20 carbon atoms, R ^10, R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms and forms a ring structure of 5 or more members with two adjacent Ns, and R ¹⁵ and R ¹⁶ are hydrocarbon groups having 1 to 20 carbon atoms, active hydrogen 1 is a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no carbon atom, or 3 organic substituted silyl groups, and m is an integer of 2 or 3.

In the general formula (6), A ² is a monovalent group having at least one functional group selected from tertiary amine, pyridine, cyan, and imine, and R ¹ and R ² are each independently , An alkyl group having 1 to 20 carbon atoms or an aryl group, and R ⁸ is an alkylene group having 1 to 20 carbon atoms. m is an integer of 2 or 3.

In the general formula (7), R ¹ , R ² and R ⁶ each independently represent an alkyl group or aryl group having 1 to 20 carbon atoms, and R ⁸ represents an alkylene group having 1 to 20 carbon atoms. . R ³ , R ⁴ and R ⁵ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other and together with the silicon atom to which they are bonded. To form a ring. m is an integer of 1 to 2, and f is an integer of 1 to 10.

In the general formula (8), R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group, and R ⁸ represents an alkylene group having 1 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other and together with the silicon atom to which they are bonded. but it may also form a ring Te.

[5]
A modified conjugated diene polymer obtained by the method for producing a modified conjugated diene polymer according to any one of [1] to [4].

[6]
A modified conjugated diene polymer composition containing 0.5 to 300 parts by mass of a silica-based inorganic filler with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer according to [5].

[7]
For 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer described in [5] above,
The modified conjugated diene polymer composition according to [6], further containing 0.5 to 100 parts by mass of carbon black.
[8]
A tire comprising the modified conjugated diene polymer composition according to [6] or [7].

  According to the present invention, when a vulcanizate containing a silica-based inorganic filler is used, it has an excellent balance between low hysteresis loss and safety-related characteristics such as wet skid resistance and low temperature characteristics, and has practically sufficient resistance. A modified conjugated diene polymer composition having wearability and fracture strength and satisfying good processability, a tire containing the modified conjugated diene polymer composition, and the modified conjugated diene polymer composition Modified conjugated diene-based polymer and a method for producing the same are obtained.

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

[Method for producing modified conjugated diene polymer]
The method for producing the modified conjugated diene polymer of the present embodiment is as follows:
Polymerizing a conjugated diene compound or a conjugated diene compound with a polyfunctional anionic polymerization initiator having a molecular weight distribution measured using gel permeation chromatography (GPC) in the range of 1.2 to 3.5 Obtaining a conjugated diene polymer obtained by copolymerizing with an aromatic vinyl compound;
At the polymerization active terminal of the conjugated diene polymer,
(I) a step in which the total number of alkoxy groups bonded to the silyl group is 4 or more and the modifier (A) having one or more nitrogen atoms is reacted;
(II) a step of reacting a modifying agent (B) in which the total number of alkoxy groups bonded to the silyl group is 2 or 3, and having one or more nitrogen atoms;
Have

(Polymerization process)
In the method for producing a modified conjugated diene polymer of the present embodiment, as a previous step of the modification step, first, a conjugated diene polymer is produced using a predetermined polyfunctional anionic polymerization initiator.
The polyfunctional anionic polymerization initiator used in the step of polymerizing the conjugated diene polymer will be described.

<Polyfunctional anionic polymerization initiator>
A polyfunctional anionic polymerization initiator can be prepared by reacting a polyvinyl aromatic compound and an organic lithium compound.
For example, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting a polyvinyl aromatic compound, an organolithium compound and a monovinyl aromatic A method of reacting a polyvinyl aromatic compound after reacting with an aromatic compound, a method of reacting an organolithium compound in the presence of two or three of a conjugated diene compound and / or a monovinyl aromatic compound and a polyvinyl aromatic compound, etc. Is mentioned.
In particular, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting the polyvinyl aromatic compound, a conjugated diene compound and polyvinyl aroma. A polyfunctional anion initiator prepared by a method of reacting a monoorganolithium compound in the presence of a group compound is preferred.
In addition, in order to promote and stabilize the formation of the polyfunctional anionic polymerization initiator, it is preferable to add a Lewis base into the system during the preparation.

[Polyvinyl aromatic compounds]
Examples of the polyvinyl aromatic compound used for the preparation of the polyfunctional anionic polymerization initiator include o, m and p-divinylbenzene, o, m and p-diisopropenylbenzene, 1,2,4-trivinylbenzene, 1 , 2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4'-trivinylbiphenyl, 1,2 -Divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene and the like.
These may be used alone or in combination of two or more.
In particular, divinyl benzene and diisopropenyl benzene are preferable, and a mixture of these o-, m-, and p-isomers may be used. For industrial use, it is economically advantageous to use a mixture of these isomers.

[Conjugated diene compounds and monovinyl aromatic compounds]
For the preparation of the polyfunctional anionic polymerization initiator, a conjugated diene compound and / or a monoaromatic vinyl compound may be used together with the polyvinyl aromatic compound.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, Examples include 1,3-hexadiene, and 1,3-butadiene and isoprene are particularly preferable.
Examples of the monovinyl aromatic compound include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and styrene is particularly preferable.
The conjugated diene compound and / or monoaromatic vinyl compound is preferably added so that the polyfunctional anionic polymerization initiator measured by GPC has a polystyrene-equivalent weight average molecular weight in the range of 500 to 20,000. More preferably, it is added so as to be 10,000 to 10,000.

[Organic lithium compounds]
Examples of the organolithium compound used for the preparation of the polyfunctional anionic polymerization initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and benzyllithium. Compound; 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4- Dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-trilithio-2,4 Polyfunctional organolithium compounds such as 6-triethylbenzene can be mentioned. In particular, a monoorganolithium compound of n-butyllithium, sec-butyllithium, or tert-butyllithium is preferable.

[solvent]
Examples of the solvent used for preparing the polyfunctional anionic polymerization initiator include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, and xylene. Group hydrocarbons and the like.

[Lewis base]
In order to promote or stabilize the formation of the polyfunctional anionic polymerization initiator, it is effective to add a Lewis base into the system during the preparation process of the polyfunctional anionic polymerization initiator.
Examples of the Lewis base include tertiary monoamine, tertiary diamine, chain or cyclic ether.
Examples of the tertiary monoamine include trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine, N, N-dimethylformamide diisopropyl acetal, N, N -Compounds such as dimethylformamide dicyclohexyl acetal.
As the tertiary diamine, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane Diamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, N′-tetramethylhexanediamine, dipiperidi And compounds such as nopentane and dipiperidinoethane.
Examples of the chain ether include dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.
Examples of the cyclic ether include tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, and 2,2-bis (2-oxolanyl). ) Butane, 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, and the like.
Among the Lewis bases, tertiary monoamine trimethylamine, triethylamine, tertiary diamine N, N, N ′, N′-tetramethylethylenediamine, and cyclic ether tetrahydrofuran, 2,2-bis (2-oxolanyl). ) Propane is preferred.
The Lewis base may be used alone or in combination of two or more.

[Lewis base addition amount]
Moreover, when adding a Lewis base when preparing a polyfunctional anionic polymerization initiator, it is preferable to add within a range of 30 to 50,000 ppm with respect to the solvent used when preparing the polymerization initiator, It is more preferable to add within the range of 200 to 20,000 ppm.
It is preferable to add 30 ppm or more in order to fully express the effect of promoting and stabilizing the reaction, ensuring the degree of freedom of microstructure adjustment in the subsequent polymerization step, and recovering and purifying the solvent after polymerization. In consideration of separation from the polymerization solvent in the process, it is preferable to add 50,000 ppm or less.

[Polyvinyl aromatic compounds / Organic lithium compounds]
The polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer is such that the molar ratio of the polyvinyl aromatic compound and the organic lithium is in the range of polyvinyl aromatic compound / organic lithium compound = 0.01 to 1.0. It is preferable that it is prepared as described above.
The greater the amount of the polyvinyl aromatic compound used relative to the organic lithium, the greater the proportion of molecular chain terminals to which functional groups are imparted by the modification reaction of the conjugated diene polymer described later, and the affinity with the silica particles described later. The reactivity is improved, the balance between the low hysteresis loss and the wet skid resistance in the modified conjugated diene polymer composition is improved, and the wear resistance and fracture characteristics are improved.
On the other hand, when the amount of the polyvinyl aromatic compound used is smaller than that of the organolithium compound, the workability at the time of kneading the composition can be improved, and from this point of view, it can be 1.0 mol or less. preferable.
For processability, the Mooney viscosity of the composition can be used as an index. When the Mooney viscosity of the composition is too high, adverse effects such as an increase in torque during melting and an increase in power consumption occur.
Further, it may be difficult to produce a uniform sheet in the sheeting process after kneading.
In general, when the low hysteresis loss property is improved, the Mooney viscosity of the composition tends to increase and the workability tends to deteriorate. However, it is practically important not to increase it so much from the above viewpoint.
From the viewpoint of making these balances good, the amount of the polyvinyl aromatic compound is preferably in the range of 0.02 to 1.0 mol and in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic lithium compound. Is more preferable.

[Preparation temperature and reaction time of polyfunctional anionic polymerization initiator]
The temperature for preparing the polyfunctional anionic polymerization initiator is preferably in the range of 10 ° C to 140 ° C, and more preferably in the range of 35 ° C to 110 ° C.
From the viewpoint of productivity, it is preferably 10 ° C or higher, and preferably 140 ° C or lower in order to suppress side reactions due to high temperatures.
The reaction time for preparing the polyfunctional anionic polymerization initiator depends on the reaction temperature, but is in the range of 5 minutes to 24 hours.

[Weight average molecular weight and molecular weight distribution of polyfunctional anionic polymerization initiator]
The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyfunctional anionic polymerization initiator is preferably in the range of 500 to 20,000, more preferably 1,000 to. 10,000.
The molecular weight distribution is in the range of (Mw / Mn) 1.2 to 3.5, preferably in the range of 1.2 to 2.5, and more preferably in the range of 1.2 to 2.0.
A modified conjugated diene polymer composition containing a conjugated diene polymer obtained using a polyfunctional anionic polymerization initiator having a molecular weight distribution in this range has a low Mooney viscosity, low hysteresis loss and wet skid. The resulting vulcanizate has an excellent balance of resistance.

<Polymerization of conjugated diene polymer>
In order to obtain the modified conjugated diene polymer of the present embodiment, the conjugated diene polymer before modification is obtained by polymerizing a conjugated diene compound using the polyfunctional anionic polymerization initiator described above, or conjugated diene compound and aromatic. It is obtained by copolymerizing with a vinyl compound.
Hereinafter, the polymer before modification for obtaining the modified conjugated diene polymer of this embodiment is referred to as a “conjugated diene polymer”, which is conjugated with a polymer obtained by polymerizing only the conjugated diene compound. Both a diene compound and a copolymer obtained by copolymerizing an aromatic vinyl compound are included.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like can be mentioned. These may be used alone or in combination of two or more. Preferred conjugated diene compounds include 1,3-butadiene and isoprene.
Examples of the aromatic vinyl compound include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and the like. These may be used alone or in combination of two or more. Styrene is mentioned as a preferable aromatic vinyl compound.

The conjugated diene polymer may be a random copolymer or a block copolymer.
Examples of the random copolymer include a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, and a butadiene-isoprene-styrene random copolymer.
The composition distribution of each monomer in the copolymer chain includes a completely random copolymer having a statistically random composition, or a tapered random copolymer having a tapered composition distribution.
The bonding mode of the conjugated diene, that is, the composition of 1,4-bonds and 1,2-bonds may be uniform or distributed.

Examples of the block copolymer include a 2-type block copolymer having 2 blocks, a 3-type block copolymer having 3 blocks, and a 4-type block copolymer having 4 blocks.
For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. And an S—B2 type block copolymer, an S—B—S3 type block copolymer, a S—B—S—B4 type block copolymer, and the like.
In the above equation, the boundaries of each block need not be clearly distinguished.
When the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. In the block B, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or a plurality of portions where the aromatic vinyl compound is distributed in a tapered shape may coexist. In the block B, a plurality of segments having different aromatic vinyl compound contents may coexist. When a plurality of blocks S and blocks B are present in the block copolymer, the structures such as molecular weight and composition thereof may be the same or different.

More generally, examples of the block copolymer include structures represented by the following general formula.
(SB) _n , S- (BS) _n , B- (SB) _n , (SB) _m- X,
[(SB) _n ] _m- X, [(BS) _n- B] _m- X, [(SB) _n- S] _m- X
(N is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X is the residue of the coupling agent or the remainder of the polyfunctional initiator. The structure of the polymer chain bonded to X may be the same or different.)
The conjugated diene polymer that is a state before the modification of the modified conjugated diene polymer of the present embodiment may be any mixture having the structure represented by the above general formula.

The conjugated diene polymer is obtained by growing by the anionic polymerization reaction using the polyfunctional anionic polymerization initiator described above. In particular, a (co) polymer having an active end obtained by a growth reaction by living anionic polymerization is more preferable. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained by a modification step described later.
Although it does not specifically limit as a polymerization mode, It can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. The reactor may be a tank type with a stirrer, a tube type, or the like.

The modified conjugated diene polymer, which is in a state after undergoing the modification step described later, is a hydrogenated conjugated diene polymer in which all or part of the double bonds of the conjugated diene polymer are converted to saturated hydrocarbons after modification. There may be.
A polymer in which all or a part of such double bonds are converted to saturated hydrocarbons has improved heat resistance and weather resistance, and therefore can prevent deterioration of the product when processed at a high temperature. The molecular mobility can be changed or the compatibility with other polymer compounds can be improved.
As a result, it is preferable because it exhibits excellent performance in various applications such as automobile applications.
More specifically, the hydrogenation rate (that is, the hydrogenation rate) of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose, and is not particularly limited. When obtaining a polymer having good heat aging resistance and weather resistance, the hydrogenation rate of the unsaturated double bond based on the conjugated diene compound in the (co) polymer is preferably more than 70%. More preferably, it is 75% or more, more preferably 85% or more, and still more preferably 90% or more. For improving the thermal stability, molecular mobility or compatibility with the resin, the hydrogenation rate in the (co) polymer is preferably 3% to 70%, more preferably 5% to 65%, Preferably, it is 10% to 60%.
The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but the hydrogenation rate is preferably 50% or less. More preferably, it is 30% or less, and further preferably 20% or less.
The above hydrogenation rate can be measured by a nuclear magnetic resonance apparatus (NMR).

As a hydrogenation method, a known method can be used.
A particularly suitable hydrogenation method is a method in which gaseous hydrogen is blown into the polymer solution in the presence of a catalyst.
As the catalyst, a heterogeneous catalyst, a catalyst in which a noble metal is supported on a porous inorganic substance, a homogeneous catalyst, a catalyst in which a salt such as nickel or cobalt is solubilized and reacted with organoaluminum, etc., a metallocene such as titanocene And the like. Of these, a titanocene catalyst capable of selecting mild hydrogenation conditions is particularly preferable. Also, hydrogenation of the aromatic group is possible by using a noble metal supported catalyst.
For example, as a catalyst for hydrogenating unsaturated double bonds based on conjugated diene compounds, (1) supported heterogeneous systems in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. (2) a so-called Ziegler type hydrogenation catalyst using (2) an organic acid salt such as Ni, Co, Fe, Cr, or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum; Examples include so-called organometallic complexes such as organometallic compounds such as Ru, Rh, and Zr. Specific examples include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-5. The hydrogenation catalyst described in Japanese Patent Application Laid-Open No. 9041 and Japanese Patent Application Laid-Open No. 8-109219 can be used. A preferred hydrogenation catalyst is a reaction mixture of a titanocene compound and a reducing organometallic compound.

  If the conjugated diene compound contains allenes, acetylenes or the like as impurities, there is a risk of inhibiting the modification reaction described later. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and further preferably 50 ppm or less in the conjugated diene compound. Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

The polymerization reaction of the conjugated diene polymer described above is preferably performed in a solvent.
Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons.
Specifically, 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; Examples thereof include hydrocarbons composed of a mixture thereof.
Treatment of allenes and acetylenes, which are impurities, with an organometallic compound before being subjected to a polymerization reaction tends to yield a polymer having a high concentration of active terminals, and a high modification rate is achieved. It is preferable because of its tendency.

In the polymerization reaction of a conjugated diene polymer, for the purpose of randomly copolymerizing an aromatic vinyl compound with a conjugated diene compound, as a vinylating agent for controlling the microstructure of the conjugated diene part, or improving the polymerization rate, etc. For this purpose, a small amount of a polar substance may be added.
Examples of polar substances include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl) propane; tetramethylethylenediamine And tertiary amine compounds such as dipiperidinoethane, trimethylamine, triethylamine, pyridine and quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate and sodium amylate; A phosphine compound such as triphenylphosphine can be used. These polar substances may be used alone or in combination of two or more.
The addition amount of a polar substance is not specifically limited, It selects according to the objective and the grade of an effect. Usually, 0.01-100 mol is preferable with respect to 1 mol of polymerization initiators.
Such a polar substance (vinylating agent) can be used in an appropriate amount according to the desired vinyl bond amount as a regulator of the microstructure of the polymer conjugated diene moiety.
Many polar substances have an effective randomizing effect at the same time in copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, a part of 1,3-butadiene is intermittently produced during the copolymerization as described in JP-A-59-140221. You may use the method of adding.

  The polymerization temperature of the conjugated diene polymer is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, it is preferably 0 ° C. or higher, and the modifier for the active terminal after the completion of polymerization. From the viewpoint of sufficiently securing the reaction amount, it is preferably 120 ° C. or lower.

The amount of bonded aromatic vinyl in the conjugated diene polymer is not particularly limited, but is preferably 5 to 70% by mass, and more preferably 10 to 50% by mass.
When the amount of bonded aromatic vinyl is within the above range, a vulcanizate having a further excellent balance between low hysteresis loss and wet skid resistance and satisfying wear resistance and fracture strength can be obtained.
Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it can measure by the method according to the Example mentioned later.

Further, when the conjugated diene polymer is a copolymer of a conjugated diene compound and an aromatic vinyl compound, it is preferable that the number of blocks in which 30 or more aromatic vinyl units are linked is small or absent. .
Specifically, when the conjugated diene polymer is a butadiene-styrene copolymer, the method described in Kolthoff's method (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In the known method for decomposing a conjugated diene polymer and analyzing the amount of polystyrene insoluble in methanol, the block in which 30 or more aromatic vinyl units are linked is preferably 5% by mass with respect to the polymer amount. Hereinafter, it is more preferably 3% by mass or less.

Moreover, the amount of vinyl bonds in the conjugated diene bond unit of the modified conjugated diene polymer is not particularly limited, but is preferably 10 to 75 mol%, and more preferably 25 to 65 mol%.
When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between low hysteresis loss and wet skid resistance and satisfying wear resistance and fracture strength can be obtained.
Here, when the modified conjugated diene polymer is a copolymer of butadiene and styrene, the butadiene bond unit in the butadiene bond unit is obtained by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). A vinyl bond amount (1,2-bond amount) can be determined.
Low hysteresis when the microstructure (the amount of each bond in the modified conjugated diene polymer) is in the above range, and the glass transition temperature of the modified conjugated diene polymer is in the range of −45 to −15 ° C. It is possible to obtain a vulcanizate with an even better balance between loss and wet skid resistance.
Regarding the glass transition temperature, according to ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Infection point) of the DSC differential curve is defined as the glass transition temperature.

(Modification process)
After obtaining the conjugated diene polymer by the method described above, the total number of (I) alkoxy groups bonded to the silyl group at the active end is 4 or more, and the modifier (A) has one or more nitrogen atoms. And (II) a step in which the total number of alkoxy groups bonded to the silyl group is 2 or 3, and a modifier (B) having one or more nitrogen atoms is reacted. The modified conjugated diene polymer is obtained.

<Modifier>
As the modifier (A) used in the modification step (I), the total number of alkoxy groups bonded to the silyl group is 4 or more and having one or more nitrogen atoms, for example, the following general formula (1) or General formula (2) is mentioned.

(In General Formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ represent an alkylene group having 1 to 20 carbon atoms. M is an integer of 1 or 2, and n is an integer of 2 or 3. In the compound represented by the general formula (1), the total number of alkoxy groups having 1 to 20 carbon atoms is 4. That's it.)

Examples of the modifying agent represented by the general formula (1) include 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-trimethoxy Silylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl -1- (3-Dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclo Examples include pentane.
Among these, m is 2, from the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability of the modified conjugated diene polymer composition of the present embodiment. Those in which n is 3 are preferred. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is preferred.

(In General Formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group, and R ⁸ and R ⁹ are each an alkylene group having 1 to 20 carbon atoms. is there.
When a plurality of R ⁸ , R ⁹ and A ¹ are present, they may be the same or different. m and n are each an integer of 0 to 3.
p is an integer of 0 to 20, and when p is 2 or more, the plurality of repeating units represented by (R ⁹ -A ¹ -R ⁸ ) may be different from each other. In the compound represented by the general formula (2), the total number of alkoxy groups having 1 to 20 carbon atoms is 4 or more. A ¹ is a group represented by any one of the following general formulas (a), (b), and (c). )

(In the general formula (a), R ¹⁰ and R ¹¹ are alkylene groups having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)

(In the general formula (b), R ⁷ is an alkyl group or aryl group having 1 to 20 carbon atoms, an active hydrogen as an aryl group, and a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen. Or 3 organic substituted silyl groups.)

(In the general formula (c), R ¹⁰ is an alkylene group having 1 to 20 carbon atoms, R ⁵ and R ⁶ is an alkyl group or an aryl group having 1 to 20 carbon atoms .r is an integer of 0 to 3 is there.)

Examples of the modifier represented by the general formula (2) include the following compounds.
That is, A ¹ in the general formula (2) is, for example, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [ 3- (triethoxysilyl) propyl] piperazine, 1,4-bis [3- (dimethoxymethylsilyl) propyl] piperazine, 1,3-bis [3- (trimethoxysilyl) propyl] imidazolidine, 1,3- Bis [3- (triethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (diemethoxyethylsilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydro Pyrimidine, 1,3-bis [3- (triethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- (tributoxysilyl) pro Le] -1,2,3,4-tetrahydropyrimidine-like.
Examples of the compound represented by the following general formula (b) in which A ¹ in the general formula (2) is bis (3-triethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) ethylamine, Bis (3-triethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) benzylamine, bis (tri Corresponding to ethoxysilylmethyl) methylamine, bis (2-triethoxysilylethyl) methylamine, bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine and their triethoxysilyl compounds Trimethoxysilyl compound, bis ( - trimethoxysilylpropyl) N- trimethylsilyl amine, bis (3-triethoxysilylpropyl) N- trimethylsilyl amine, bis (2-triethoxysilyl ethyl) N- trimethylsilyl amine compounds, and the like.
Furthermore, A ¹ in the general formula (2) is, for example, tris (triethoxysilylmethyl) amine, tris (2-triethoxysilylethyl) amine, tris (3) as a compound of the following general formula (c). -Triethoxysilylpropyl) amine and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds.
Among these, from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability of the modified conjugated diene polymer composition of the present embodiment, m and n Is preferably 3. Specifically, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, bis (3-trimethoxysilylpropyl) N— Trimethylsilylamine, bis (3-triethoxysilylpropyl) N-trimethylsilylamine, bis (3-triethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) ethylamine, and tris (triethoxysilylmethyl) amine are preferred. .

  The total number of alkoxy groups bonded to the silyl group used in the modification step (II) is 2 or 3, and the modifier (B) having one or more nitrogen atoms includes, for example, the following general formula (3) , General formula (4), general formula (5), general formula (6), general formula (7), and compounds represented by general formula (8).

(In the general formula ^{(3), R 1, R} 2 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ^8, R ⁹ represents an alkylene group having 1 to 20 carbon atoms , R ¹² , R ¹³ and R ¹⁴ are each a hydrocarbon group having 1 to 20 carbon atoms which contains Si, O, or N and may be substituted with an organic group having no active hydrogen. Is an integer.)

Examples of the compound represented by the general formula (3) include N- [2- (trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine, N- [2- (Dimethoxymethylsilanyl) -ethyl] -N-ethyl-N ′, N′-dimethylethane-1,2-diamine, N- [3- (trimethoxysilanyl) -propyl] -N, N ', N'-trimethylpropane-1,3-diamine, N- [3- (dimethoxymethylsilanyl) -propyl] -N-ethyl-N', N'-dimethylpropane-1,3-diamine, N- [3- (Triethoxysilanyl) -propyl] -N, N ′, N′-triethyl-2-methylpropane-1,3-diamine, N- [3- (dimethoxymethylsilanyl) -propyl] -2 , N, N ′, N′-tetramethylpropane-1 3-diamine, N- (2-dimethylaminoethyl) -N ′-[2- (trimethoxysilanyl) -ethyl] -N, N′-dimethylethane-1,2-diamine, N- [2- ( Diethoxypropylsilanyl) -ethyl] -N ′-(3-ethoxypropyl) -N, N′-dimethylethane-1,2-diamine, N- [2- (trimethoxysilanyl) -ethyl] -N '-Methoxymethyl-N, N'-dimethylethane-1,2-diamine, N- [2- (trimethoxysilanyl) -ethyl] -N, N'-dimethyl-N'-(2-trimethylsilanyl Ethyl) -ethane-1,2-diamine, N- [2- (triethoxysilanyl) -ethyl] -N, N′-diethyl-N ′-(2-dibutylmethoxysilanylethyl) -ethane-1, 2-diamine etc. are mentioned.
A preferred compound is N- [2- (trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine.
A composition containing a modified conjugated diene polymer modified with this compound is particularly excellent in the balance of wet skid characteristics, low hysteresis loss, wear resistance, and fracture strength when vulcanized.

(In General Formula (4), R ¹ and R ² are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, R ⁹ is an alkylene group having 1 to 20 carbon atoms, R ¹⁰ , R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms and has a ring structure of 5 or more members with two adjacent N atoms, and R ¹⁴ has no hydrocarbon group having 1 to 20 carbon atoms and active hydrogen. (It is a C1-C20 hydrocarbon group substituted by a hetero atom, or a 3 organic substituted silyl group, and m is an integer of 2 or 3.)

Examples of the compound represented by the general formula (4) include 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) propyl] -4- Methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) propyl] -3-ethylimidazolidine, 1- [3- (triethoxy) Silyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilyl) propyl] -1-methyl-1 , 2,3,4-Tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) propyl] -1-ethyl-1,2,3,4-teto Hydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) propyl] imidazolidine, (2- {3- [3- (trimethoxysilyl) propyl] tetrahydropyrimidin-1-yl} Ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (dimethoxymethylsilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (Tributoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (diethoxyethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [3- (dimethoxymethylsilyl) (Lopyl) -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [4- (triethoxysilyl) butyl] -4- ( And trimethylsilyl) piperazine.
Among these, 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (triethoxysilyl) Propyl] -3-methylhexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine is preferably used, and 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (Triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine is more preferred.

(In General Formula (5), R ¹ and R ² are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, R ⁹ is an alkylene group having 1 to 20 carbon atoms, R ¹⁰ , R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms and forms a ring structure of 5 or more members with two adjacent Ns, and R ¹⁵ and R ¹⁶ are hydrocarbon groups having 1 to 20 carbon atoms, active hydrogen A hydrocarbon group having 1 to 20 carbon atoms or a 3 organic substituted silyl group substituted with a heteroatom having no carbon atom, and m is an integer of 2 or 3.)

Examples of the compound represented by the general formula (5) include 2- [3- (trimethoxysilyl) propyl] -1,3-dimethylimidazolidine, 2- (diethoxyethylsilyl) -1,3- Diethylimidazolidine, 2- (triethoxysilyl) -1,4-diethylpiperazine, 2- (dimethoxymethylsilyl) -1,4-dimethylpiperazine, 5- (triethoxysilyl) -1,3-dipropylhexahydro Pyrimidine, 5- (diethoxyethylsilyl) -1,3-diethylhexahydropyrimidine, {2- [3- (2-dimethylaminoethyl) -2- (ethyldimethoxysilyl) -imidazolidin-1-yl]- Ethyl} -dimethylamine, 5- (trimethoxysilyl) -1,3-bis- (2-methoxyethyl) -hexahydropyrimidine, -(Ethyldimethoxysilyl) -1,3-bis- (2-trimethylsilylethyl) -hexahydropyrimidine) -1,3-dimethylimidazolidine, 2- (3-diethoxyethylsilyl-propyl) -1,3 -Diethylimidazolidine, 2- (3-triethoxysilyl-propyl) -1,4-diethylpiperazine, 2- (3-dimethoxymethylsilyl-propyl) -1,4-dimethylpiperazine, 5- (3-triethoxy Silyl-propyl) -1,3-dipropylhexahydropyrimidine, 5- (3-diethoxyethylsilyl-propyl) -1,3-diethylhexahydropyrimidine, {2- [3- (2-dimethylaminoethyl) -2- (3-Ethyldimethoxysilyl-propyl) -imidazolidin-1-yl] -ethyl} -dimethyla 5- (3-trimethoxysilyl-propyl) -1,3-bis- (2-methoxyethyl) -hexahydropyrimidine, 5- (3-ethyldimethoxysilyl-propyl) -1,3-bis- ( 2-trimethylsilylethyl) -hexahydropyrimidine, 2- [3- (trimethoxysilyl) propyl] -1,3-bis (trimethylsilyl) imidazolidine, 2- (diethoxyethylsilyl) -1,3-bis (triethyl) Silyl) imidazolidine, 2- (triethoxysilyl) -1,4-bis (trimethylsilyl) piperazine, 2- (dimethoxymethylsilyl) -1,4-bis (trimethylsilyl) piperazine, 5- (triethoxysilyl) -1 , 3-bis (tripropylsilyl) hexahydropyrimidine and the like.
Among these, 2- [3- (trimethoxysilyl) propyl] -1,3-dimethylimidazolidine and 2- [3- (trimethoxysilyl) propyl] -1,3- (bistrimethylsilyl) imidazolidine are preferable. .

(In General Formula (6), A ² is a monovalent group having at least one functional group selected from tertiary amine, pyridine, cyan, and imine, and R ¹ and R ² are each independently And R ⁸ is an alkylene group having 1 to 20 carbon atoms, and m is an integer of 1 to 3).

Examples of the compound represented by the general formula (6) include [3- (1-hexamethyleneimino) propyl] triethoxysilane, [(1-hexamethyleneimino) methyl] triethoxysilane, [2- (1-hexamethyleneimino) ethyl] triethoxysilane, [3- (1-pyrrolidinyl) propyl] triethoxysilane, [3- (1-heptamethyleneimino) propyl] triethoxysilane, [3- (1-dodeca Methyleneimino) propyl] triethoxysilane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 3- [10- (triethoxysilyl) decyl] -4-oxazoline and their triethoxy Trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds corresponding to silyl compounds Methyldimethoxysilyl compounds, ethyl dimethoxy silyl compounds, and the like.
[3- (dimethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [2- (dimethylamino) ethyl] triethoxysilane, [3- (dibutylamino) propyl] tri Ethoxysilane, [(3-methyl-3-ethylamino) propyl] triethoxysilane and trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds corresponding to these triethoxysilyl compounds And ethyldimethoxysilyl compounds.
Furthermore, 2- (triethoxysilylethyl) pyridine and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds and the like can be mentioned. It is done. 2-cyanoethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 11-cyanoundecyltriethoxysilane and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, Examples thereof include a methyldimethoxysilyl compound and an ethyldimethoxysilyl compound.
Of these, 3-cyanopropyltriethoxysilane is preferred.
In the general formula (6), when A ² contains imine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3 -(Triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propane Amines, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and Trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilanes corresponding to these triethoxysilyl compounds Le compounds, ethyl dimethoxy silyl compounds, and the like.

In (formula ^{(7), R 1, R} 2, R 6 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁸ represents an alkylene group having 1 to 20 carbon atoms .
R ³ , R ⁴ and R ⁵ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other and together with the silicon atom to which they are bonded. To form a ring. m is an integer of 1 to 2, and f is an integer of 1 to 10. )

  Examples of the compound represented by the general formula (7) include N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, and triethoxysilyl compounds thereof. And trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds, and the like.

In (formula ^{(8), R 1, R} 2 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁸ is .R ³ representing an alkylene group having 1 to 20 carbon atoms , R ⁴ and R ⁵ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other to form a ring together with the silicon atom to which they are bonded. M is an integer of 1 to 2)

  Examples of the compound represented by the general formula (8) include 1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane and dimethoxysilyl compounds corresponding to these diethoxysilyl compounds, methyl Examples thereof include an ethoxysilyl compound, an ethylethoxysilyl compound, a methylmethoxysilyl compound, and an ethylmethoxysilyl compound.

The modification reaction of the conjugated diene polymer using the above-described modifier will be described.
In the modification reaction, the above-described modifiers may be used alone or in combination of two or more.

<Modification reaction temperature, modification reaction time>
There are no particular restrictions on the reaction temperature, reaction time, and the like when the above-described modifier is reacted with the polymerization active terminal of the conjugated diene polymer. It is preferable to make it.

<Addition amount of modifier>
The total number of alkoxy groups bonded to the silyl group used in the above-described (I) modification step is 4 or more and the modification agent (A) having one or more nitrogen atoms is contained in the added modification agent (A). Add so that the total number of moles of the alkoxy group bonded to the silyl group (Aa) is in the range of 0.05 to 2 times the total number of moles of lithium contained in the polyfunctional anionic polymerization initiator described above. Is more preferable, and it is more preferable to add so that it may become the range of 0.1-1 times, and it is still more preferable to add so that it may become the range of 0.1-0.8 times.

  The number of active lithium terminals per molecule of a conjugated diene polymer obtained by polymerization using a polyfunctional anionic polymerization initiator exceeds 1 on average. Therefore, by reacting with 4 or more alkoxy groups, a very high molecular weight component is generated and the wear resistance can be improved. From the viewpoint of controlling the high molecular weight component and not impairing the workability, the modifier (A) has a large total number of moles (Aa) of alkoxy groups in the added modifier (A). The total number of moles of lithium contained in the functional anionic polymerization initiator is preferably 2 times or less. Further, from the viewpoint of obtaining a predetermined modification rate and leaving an alkoxy group at the end of the modified conjugated diene molecular chain, the modifier (A) is an alkoxy group bonded to a silyl group in the added modifier. The total number of moles (Aa) is preferably 0.05 times or more of the total number of moles of lithium contained in the polyfunctional anionic polymerization initiator described above.

  The modifier (B) used in the above-described (II) modification step, wherein the total number of alkoxy groups bonded to the silyl group is 2 or 3, and has one or more nitrogen atoms, is in the added modifier (B). It is added so that the total number of moles (Ba) of the alkoxy groups bonded to the silyl group is in the range of 0.3 to 3 times the total number of moles of lithium contained in the polyfunctional anionic polymerization initiator described above. It is preferable that it is added in a range of 0.5 to 2 times.

  As described above, the number of active lithium terminals per molecule of a conjugated diene polymer obtained by polymerization using a polyfunctional anionic polymerization initiator exceeds 1 on average. Therefore, a high molecular weight component is produced by reacting with 2 or 3 alkoxy groups. From the viewpoint of controlling the high molecular weight component and not impairing the workability, the modifier (B) has a large total number of alkoxy groups (Ba) in the added modifier (B). More preferably, it is 3 times or less the total number of moles of lithium contained in the functional anionic polymerization initiator. Further, from the viewpoint of obtaining a predetermined modification rate and leaving an alkoxy group at the end of the modified conjugated diene molecular chain, the modifier (B) is bonded to the silyl group in the added modifier (B). It is preferable that the total number of moles (Ba) of the alkoxy group is 0.3 times or more the total number of moles of lithium contained in the polyfunctional anionic polymerization initiator described above.

  The ratio of the modifier (A) to the modifier (B) to be added is in the range of 0.05 to 0.5 in terms of a molar ratio of (A−a) / [(A−a) + (B−a)]. Is more preferable, and 0.1 to 0.3 is more preferable. It is preferable to add so that it may become 0.5 or less from a viewpoint of workability.

  The order in which the modifier (A) and the modifier (B) are added is not particularly limited, and the method of adding the modifier (B) after adding the modifier (A), after adding the modifier (B). A method of adding the modifier (A), a method of adding a mixture of the modifier (A) and the modifier (B), and the like are selected.

<Modification rate>
The content of the polymer having a functional group component in the modified conjugated diene polymer, that is, the modification rate is low when the composition using the modified conjugated diene polymer of this embodiment is a vulcanized product. In order to obtain a good balance between loss and wet skid resistance and to obtain practically sufficient wear resistance and fracture characteristics, it is preferably 60% by mass or more, and more preferably 80% by mass or more. More preferably, it is more preferably 90% by mass or more.
The modification rate is to obtain a modification rate of 60% by mass or more as described above by controlling the concentration of allenes and acetylenes which are impurities in the conjugated diene compound, the treatment method thereof, and the polymerization temperature. Can do.
As a method for measuring the content of the polymer having a functional group component, that is, the modification rate, a measurement method by chromatography capable of separating the functional group-containing modified component and the non-modified component is preferable.
As a measurement method by this chromatography, a gel permeation chromatography (GPC) column using a polar substance such as silica adsorbing a functional group component as a filler is used, and the internal standard of the non-adsorbed component is quantified by comparison. The method is preferred.

The weight average molecular weight (GPC measurement: in terms of polystyrene) of the modified conjugated diene copolymer of the present embodiment obtained through the above-described modification reaction is preferably 100,000 to 2,000,000 in view of processability and physical properties, and 200,000. To 1 million is more preferable, and 250,000 to 500,000 is more preferable.
When a conjugated diene polymer is polymerized by a batch process, a plurality of peaks are observed in the molecular weight distribution of GPC. The peak on the lowest molecular weight side is mainly considered to be a component generated by polymerization initiated by a monofunctional component mixed in the polyfunctional anionic polymerization initiator. In addition, as the amount of the high molecular weight produced due to the polyfunctional component in the polyfunctional anionic polymerization initiator increases, the physical properties such as low hysteresis loss and wear resistance are improved, but the workability deteriorates. Considering processability and physical properties, the peak area on the lowest molecular weight side is preferably 10 to 70%.
By adjusting the molar ratio of the polyvinyl aromatic compound and the organolithium compound in preparing the polyfunctional anionic polymerization initiator and the addition amount of the modifier within the aforementioned range, the lowest molecular weight as described above. The peak area on the side can be 10 to 70%.
By adjusting the molar ratio of the polyvinyl aromatic compound and the organolithium compound in preparing the polyfunctional anionic polymerization initiator and the addition amount of the modifier within the aforementioned range, the lowest molecular weight as described above. The peak area on the side can be 10 to 70%.

(Reaction stop processing)
After performing the modification reaction of the conjugated diene polymer with the above-described modifier, a reaction terminator may be added to the polymer solution as necessary. As the reaction terminator, usually, alcohols such as methanol, ethanol and propanol; organic acids such as stearic acid, lauric acid and octanoic acid: water and the like can be used.

(Other processing)
In addition, after the modification reaction of the conjugated diene polymer, the metals contained in the polymer may be decalcified as necessary. As a deashing method, for example, a method is used in which water, an organic acid, an inorganic acid, an oxidizing agent such as hydrogen peroxide is brought into contact with a polymer solution to extract metals, and then the aqueous layer is separated. .
Further, after the modification reaction of the conjugated diene polymer, an antioxidant may be added to the polymer solution. Examples of the antioxidant include phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers and the like.

(Polymer recovery method)
As a method for obtaining the modified conjugated diene polymer in the present embodiment from the polymer solution, a conventionally known method can be applied.
For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. A method, a method of directly devolatilizing with a drum dryer or the like can be applied.

[Modified Conjugated Diene Polymer Composition]
The modified conjugated diene polymer composition of the present embodiment is 100 parts by mass of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer described above when the total rubber component is 100 parts by mass. On the other hand, the silica type inorganic filler shall contain 0.5-300 mass parts.

(Rubber component)
The modified conjugated diene polymer composition in the present embodiment can be used as the rubber component by combining a rubbery polymer other than the modified conjugated diene polymer described above with the modified conjugated diene polymer.
<Rubber polymer other than modified conjugated diene polymer>
Examples of such rubber-like polymers include conjugated diene polymers or hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds or hydrogenated products thereof, conjugated diene compounds and vinyl compounds. Examples thereof include a block copolymer with an aromatic compound or a hydrogenated product thereof, a non-diene polymer, and natural rubber.
Specifically, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene block copolymerized Examples thereof include styrene-based elastomers such as coalescence or hydrogenated products thereof, acrylonitrile-butadiene rubber or hydrogenated products thereof.
Examples of the non-diene polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and other olefin-based elastomers, butyl rubber, brominated butyl rubber, Acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber and the like can be mentioned.
The various rubber-like polymers described above may be modified rubbers provided with functional groups.
These rubbery polymers may be used alone or in combination of two or more.
When the above-mentioned rubbery polymer is combined with the modified conjugated diene polymer in the present embodiment and used as the rubber component, these ratios are expressed as: modified conjugated diene copolymer / rubbery polymer described above. 20 / 80-100 / 0 is preferable, 30 / 70-90 / 10 is more preferable, and 50 / 50-80 / 20 is further more preferable.

(Silica-based inorganic filler)
As the silica-based inorganic filler contained in the modified conjugated diene-based polymer composition of the present embodiment, solid particles having SiO ₂ or Si ₃ Al as a main component of a structural unit can be used.
Examples thereof include inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, and the like.
Further, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used.
Among these, silica and glass fiber are preferable, and silica is more preferable.
As silica, dry silica, wet silica, synthetic silicate silica, and the like can be used. Among them, wet silica is most preferable because it has the most remarkable effect of improving fracture characteristics and wet skid resistance.
In the modified conjugated diene polymer composition of the present embodiment, from the viewpoint of obtaining practically good abrasion resistance and fracture characteristics, the nitrogen adsorption specific surface area required by the BET adsorption method of the silica-based inorganic filler is 170 to 300 m. ² / g is preferable, and 200 to 300 m ² / g is more preferable.
As described above, the content of the silica-based inorganic filler in the modified conjugated diene polymer composition is 0.5 to 300 with respect to 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer. Although it is a mass part, 5-200 mass parts is preferable and 20-100 mass parts is more preferable.
When the content of the silica-based inorganic filler is 0.5 parts by mass or more, the effect of addition can be expressed, and when it is 300 parts by mass or less, the dispersibility is not deteriorated, and the processability is high in the composition. Mechanical strength is obtained.

(Other ingredients)
<Carbon black>
Carbon black may be added to the modified conjugated diene polymer composition of this embodiment as a reinforcing filler other than the silica-based inorganic filler described above.
Carbon black of SRF, FEF, HAF, ISAF, SAF, etc. can be used as the carbon black. Carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a DBP (dibutyl phthalate) oil absorption of 80 ml / 100 g. preferable.
The content of carbon black is preferably 0.5 to 100 parts by weight, more preferably 3 to 100 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the rubber component containing 20 parts by weight or more of the modified conjugated diene polymer. Part by mass is more preferable.
In order to express performance required for applications such as tires such as dry grip performance and conductivity, 0.5 parts by mass or more is preferably added, but from the viewpoint of dispersibility, it is preferably 100 parts by mass or less.

<Metal oxide, metal hydroxide>
In addition to the silica-based inorganic filler and carbon black described above, a metal oxide or a metal hydroxide may be further added to the modified conjugated diene polymer composition of the present embodiment.
Metal oxide refers to solid particles having the chemical formula M _x O _y (M is a metal atom, x and y are each an integer of 1 to 6) as a main component, such as alumina, titanium oxide, and oxidation. Magnesium, zinc oxide, or the like can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used.
The metal hydroxide is aluminum hydroxide, magnesium hydroxide, zirconium hydroxide or the like.

<Silane coupling agent>
Moreover, in the modified conjugated diene polymer composition of the present embodiment, a silane coupling agent may be contained.
The silane coupling agent has a function to close the interaction between the rubber component and the silica-based inorganic filler, and has an affinity or binding group for each of the rubber component and the silica-based inorganic filler. ing.
Examples of the silane coupling agent include bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, and bis- [2- (triethoxy Silyl) -ethyl] -tetrasulfide and the like.
0.1-30 mass parts is preferable with respect to 100 mass parts of silica-type inorganic fillers mentioned above, as for content of a silane coupling agent, 0.5-20 mass parts is more preferable, and 1-15 mass parts is. Further preferred.
An effective use effect is obtained when the content of the silane coupling agent is 0.1 parts by mass or more with respect to 100 parts by mass of the silica-based inorganic filler, and it is not necessary to add more than 30 parts by mass. .

<Vulcanizing agent>
The modified conjugated diene copolymer composition of the present embodiment may be a vulcanized composition that has been vulcanized with a vulcanizing agent.
As the vulcanizing agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds can be used.
Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like.
The content of the vulcanizing agent is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer.
As a vulcanization method, a conventionally known method can be applied, and the vulcanization temperature can be, for example, 120 to 200 ° C, preferably 140 to 180 ° C.

<Vulcanization accelerator, vulcanization aid>
In the above vulcanization, a vulcanization accelerator may be used as necessary.
As the vulcanization accelerator, conventionally known materials can be used. For example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate And the like.
Further, as the vulcanization aid, zinc white, stearic acid or the like can be used.
The content of the vulcanization accelerator is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer.

<Rubber softener>
In order to improve processability, the modified conjugated diene polymer composition of this embodiment may be blended with a rubber softener.
As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable.
The mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain. A paraffin chain having 50% or more carbon atoms in the total carbon is called paraffinic, a naphthene ring having 30 to 45% carbon is naphthenic, and an aromatic carbon having more than 30% aromatic is aromatic. It is called a system. The rubber softener used in the present embodiment is preferably a naphthenic and / or paraffinic one.
The content of the rubber softening agent is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, and still more preferably 30 to 90 parts by weight with respect to 100 parts by weight of the rubber component containing the modified conjugated diene polymer. .
When the content of the rubber softening agent is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, the occurrence of bleed-out can be prevented and no stickiness occurs on the surface of the composition.

<Other additives>
In the modified conjugated diene-based polymer composition in the present embodiment, softeners and fillers other than those described above within the range not impairing the object of the present invention, heat resistance stabilizer, antistatic agent, weather resistance stabilizer, You may use various additives, such as anti-aging agent, a coloring agent, and a lubricant.
Specific examples of the filler include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate.
Examples of the softening agent blended as necessary to adjust the hardness and fluidity of the target product include liquid paraffin, castor oil, and linseed oil.
Known materials can be applied as the heat resistance stabilizer, antistatic agent, weather resistance stabilizer, anti-aging agent, colorant, and lubricant.

[Method for Producing Modified Conjugated Diene Polymer Composition]
A modified conjugated diene polymer by mixing a modified conjugated diene polymer with a silica-based inorganic filler and, if necessary, carbon black and other fillers, silane coupling agents, vulcanizing agents, optional additives, etc. The method for producing the composition is not particularly limited.
For example, a melt kneading method using a general blender such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc. The method of removing by heating, etc. are mentioned.
Of these, a melt kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoint of productivity and good kneading properties.
In addition, any of a method of kneading the modified conjugated diene polymer and various compounding agents at a time and a method of mixing in multiple times can be applied.

〔tire〕
The modified conjugated diene polymer composition of this embodiment can be made into a tire by vulcanization molding according to a conventional method.
Although it can be used as various tire members, it is preferably used as a tire tread material.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

[Sample analysis method]
The analysis of the sample was performed by the method shown below.
<(1) Bonded styrene content>
A sample was dissolved in chloroform to form a chloroform solution, and the amount of bound styrene (% by mass) was measured by absorption at UV254 nm by the phenyl group of styrene.
As a measuring instrument, Shimadzu Corporation UV-2450 was used.

<(2) Microstructure of the butadiene moiety (1,2-vinyl bond amount)>
In the case of a styrene-butadiene copolymer, a sample is dissolved in carbon disulfide to form a carbon disulfide solution, an infrared spectrum is measured in the range of 600 to 1000 cm ⁻¹ using a solution cell, and the absorbance at a predetermined wave number is used. For the butadiene portion according to the calculation formula of the Hampton method and, in the case of a butadiene polymer, the Morello method.
As a measuring instrument, JASCO Corporation FT-IR230 was used.

<(3) Mooney viscosity>
According to JIS K 6300, preheating was performed at 100 ° C. for 1 minute, and the viscosity after 4 minutes was measured. A smaller value indicates a lower viscosity.

<(4) Molecular weight and molecular weight distribution>
Chromatogram is measured using GPC with three columns connected with polystyrene gel as packing material, molecular weight (Mw, Mn) is determined by calibration curve using standard polystyrene, and total peak area The lowest molecular weight peak area ratio was calculated by calculating the ratio of the lowest molecular weight peak area with respect to. Tetrahydrofuran (THF) was used as the eluent.
As the column, guard column: Tosoh TSKguardcolumnHHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR were used.
The molecular weight was measured using an RI detector (HLC8020 manufactured by Tosoh Corporation) under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.
A sample was measured by dissolving 10 mg in 20 mL of THF and injecting 200 μL.

<(5) Denaturation rate>
Applying the property that the modified component is adsorbed to the GPC column using silica gel as a filler, using a sample solution containing a sample and standard polystyrene with a molecular weight of 5000 (polystyrene does not adsorb to the column), GPC (Gross column: DIOL 4.6 × 12.5 mm 5 micron, column: Zorbax PSM-1000S, PSM-300S, PSM-60S, oven temperature 40 ° C., THF flow rate 0.5 ml / min) CCP8020 series build-up type GPC system: AS-8020, SD-8022, CCPS, CO-8020, RI-8021) both chromatograms were measured using an RI detector, and the difference between them was applied to a silica column. The amount of adsorption was measured to determine the denaturation rate.
As a sample, 10 mg was dissolved in 20 mL of THF together with 5 mg of standard polystyrene, and 200 μL was injected for measurement.
As a specific procedure, the peak area of the chromatogram using the polystyrene column is set to 100, the peak area of the standard polystyrene is P2, the peak area of the standard polystyrene is P2, and the peak area of the chromatogram using the silica column is P1. Assuming 100 as a whole, the peak area of the sample was P3, the peak area of standard polystyrene was P4, and the modification rate (%) was calculated by the formula [1- (P2 × P3) / (P1 × P4)] × 100. .

[Polyfunctional anionic polymerization initiator]
(Preparation of polyfunctional anionic polymerization initiators a to c)
After washing and drying the autoclave equipped with a stirring device and jacket having an internal volume of 10 L, and purging with nitrogen, according to the conditions shown in Table 1 below, 1,3-butadiene, cyclohexane, tetrahydrofuran, divinylbenzene ( DVB) was added, and then n-butyllithium (NBL) was added and reacted at 75 ° C. for 1 hour to prepare.
For the preparation of the polyfunctional anionic polymerization initiator, a divinylbenzene mixture (manufactured by Nippon Steel Chemical Co., Ltd.) containing m-divinylbenzene, p-divinylbenzene, ethylvinylbenzene, etc. and having a divinylbenzene concentration of 57% by mass is used. It was.
About the amount of divinylbenzene in the following Table 1, since the said commercially available divinylbenzene is a mixture, the pure amount of divinylbenzene converted excluding the content of impurities was expressed.

[Example 1]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, 740 g of butadiene, 260 g of styrene, 4800 g of cyclohexane from which impurities have been previously removed, and 2,2-bis (2 -Oxolanyl) propane 0.85 g was charged into the reactor and the temperature in the reactor was maintained at 42 ° C.
The polyfunctional polymerization initiator a prepared as described above was supplied to the reactor so that the amount of lithium added was 10.5 mmol.
After the start of the reaction, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 75 ° C.
After completion of the polymerization reaction, 1.05 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was maintained at 74 ° C. for 3 minutes. The denaturation reaction was carried out.
Thereafter, 7.35 mmol of 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine was added, and a denaturing reaction was performed at a temperature condition of 70 ° C. for 3 minutes.
After adding 2.1 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping and a drying process is performed by a dryer. Then, a styrene-butadiene copolymer (sample A) having a modifying component was obtained.
As a result of analyzing Sample A, the amount of bound styrene was 26% by mass, and the amount of bound butadiene was 74% by mass.
Sample A had a Mooney viscosity of 61.
The 1,2-bond content of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 57%.
Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 89%.
The analysis results of (Sample A) are shown in Table 2 below.

[Examples 2 to 4]
The types of polyfunctional anionic polymerization initiators described above and their addition amounts, 2,2-bis (2-oxolanyl) propane, the types of modifiers and their addition amounts are adjusted as shown in Table 2 below, The production conditions were the same as (Sample A) described above, and styrene-butadiene copolymers (Sample B, Sample C, Sample D) having a modifying component were obtained.
The analysis results of (Sample B), (Sample C), and (Sample D) are shown in Table 2 below.

Example 5
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, 1000 g of butadiene from which impurities have been removed in advance, 4800 g of cyclohexane, 2,2-bis (2-oxolanyl) as a polar substance 1.01 g of propane was put into the reactor, and the temperature in the reactor was kept at 42 ° C.
The polyfunctional polymerization initiator a prepared as described above was supplied to the reactor so that the amount of lithium added was 10.5 mmol.
After the start of the reaction, the temperature inside the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 79 ° C.
After the completion of the polymerization reaction, 2.1 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was maintained at 74 ° C. for 3 minutes. The denaturation reaction was carried out.
Thereafter, 8.4 mmol of 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine was added to the reactor, and a denaturing reaction was performed for 3 minutes at a temperature of 70 ° C.
After adding 2.1 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping and a drying process is performed by a dryer. A butadiene polymer (sample E) having a modifying component was obtained.
As a result of analyzing (Sample E), the Mooney viscosity was 62. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Morero method from the measurement result using an infrared spectrophotometer was 13. Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 93%. The analysis results of (Sample E) are shown in Table 2 below.

[Comparative Example 1]
In the same manner as in [Example 1] described above, a styrene-butadiene copolymer was obtained using the polyfunctional anionic polymerization initiator a, and then modified by adding a modifier as shown in Table 2 below. A styrene-butadiene copolymer (sample F) having components was obtained.
The analysis results of (Sample F) are shown in Table 2 below.

[Comparative Example 2]
In the same manner as in [Example 1] described above, a styrene-butadiene copolymer was obtained using the polyfunctional anionic polymerization initiator b, and then modified by adding a modifier as shown in Table 2 below. A styrene-butadiene copolymer (sample G) having components was obtained.
The analysis results of (Sample G) are shown in Table 2 below.

[Comparative Example 3]
An autoclave with an internal volume of 10 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 740 g of butadiene, 260 g of styrene, 4800 g of cyclohexane from which impurities were previously removed, -0.62 g of oxolanyl) propane was charged into the reactor and the reactor internal temperature was maintained at 42 ° C.
As a polymerization initiator, a cyclohexane solution containing 7.5 mmol of n-butyllithium was supplied to the reactor. After the start of the polymerization reaction, the temperature inside the reactor started to rise due to the exotherm caused by the polymerization, and the final temperature inside the reactor reached 74 ° C.
After the completion of the polymerization reaction, 1.175 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was maintained at 74 ° C. for 3 minutes. The denaturation reaction was carried out. Thereafter, 6.24 mmol of 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine was added, and a denaturing reaction was performed at a temperature condition of 70 ° C. for 3 minutes.
After adding 2.1 g of an antioxidant (BHT) to this polymer solution, the solvent is removed by steam stripping, and a drying treatment is performed by a dryer, so that a styrene-butadiene copolymer having a modifying component (sample) H) was obtained.
The analysis results of (Sample H) are shown in Table 2 below.

  In Table 2 below, the modifiers (A1) to (A3) correspond to the modifier (A) having a total of 4 or more alkoxy groups bonded to a silyl group and having one or more nitrogen atoms. Agents (B1) to (B3) correspond to the modifier (B) having 2 or 3 alkoxy groups bonded to a silyl group and having one or more nitrogen atoms.

(Production of modified conjugated diene polymer composition)
[Examples 6 to 10, Comparative Examples 4 to 6]
Using the samples shown in Table 2 (samples A to G) as raw rubber, modified conjugated diene polymer compositions containing the raw rubbers were obtained according to the formulation shown in Table 3 below.

The modified conjugated diene polymer composition was kneaded by the following method.
Using a closed kneading machine (with an internal volume of 0.3 liters) equipped with a temperature control device, as the first stage kneading, under the conditions of a filling rate of 65% and a rotor rotational speed of 50/57 rpm, the raw rubber (sample A to sample) G, natural rubber), filler (silica, carbon black), organosilane coupling agent, process oil, zinc white, and stearic acid.
At this time, the temperature of the closed mixer was controlled, and the modified conjugated diene polymer composition was obtained at a discharge temperature (formulation) of 155 to 160 ° C.
Next, as the second stage kneading, the blend obtained above was cooled to room temperature, an anti-aging agent was added, and kneaded again to improve silica dispersion. Also in this case, the discharge temperature (formulation) was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer.
After cooling, as a third stage of kneading, sulfur and a vulcanization accelerator were added and kneaded with an open roll set at 70 ° C.
Then, it shape | molded and vulcanized with the vulcanization press for 20 minutes at 160 degreeC.
After vulcanization, the physical properties of the modified conjugated diene polymer composition were measured.
The physical property measurement results are shown in Table 4 below.
The physical properties of the modified conjugated diene polymer composition were measured by the methods shown below.

<Bound rubber amount>
Formulation after completion of the second stage kneading step: About 0.2 gram was cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the weight was measured.
Then, after being immersed in toluene for 24 hours, a drying treatment was performed and the weight was measured.
The amount of rubber bound to the filler (modified conjugated diene polymer + natural rubber) was calculated from the amount of the undissolved component, and the ratio of the rubber bound to the filler to the amount of rubber in the first blend was determined.
The larger the value, the more bound rubber.

<Formulation Mooney viscosity>
Using a Mooney viscometer, according to JIS K6300-1, the composition after the third stage kneading step was preheated at 130 ° C. for 1 minute, and then the rotor was rotated at 2 revolutions per minute to determine the viscosity after 4 minutes. It was measured.
The smaller the value, the smaller the viscosity and the better the workability.

<Tensile strength>
The vulcanized test piece was measured by the tensile test method of JIS K6251.
The larger the index value, the better the fracture resistance.

<Viscoelastic parameters>
Using a viscoelasticity tester (ARES) manufactured by Rheometrics Scientific, the viscoelastic parameters of the vulcanized specimens were measured in torsion mode.
Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip performance. The larger the index value, the better the wet grip performance.
Further, tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel saving characteristics. The smaller the index value, the better the fuel saving performance.
Further, the difference in storage elastic modulus (G ′) between strains of 0.1% and 10% was used as an index of the Payne effect as ΔG ′. The smaller the index value, the better the dispersibility of the filler such as silica.

<Abrasion resistance>
Using an Akron abrasion tester, according to JIS K6264-2, the wear amount of the vulcanized test piece at a load of 44.1 N and 1000 revolutions was measured and indexed.
The larger the index value, the better the wear resistance.

As shown in Table 4 above, the modified conjugated diene polymer compositions of Examples 6 to 10 using (Samples A to E) described above are those of Comparative Examples 4 to 6 using Samples F, G, and H. When compared with the composition, the amount of bound rubber in the silica compounded composition is increased, the Payne effect is small and the dispersibility of the silica is excellent, and the high temperature tan δ is greatly reduced. It has been found that low rolling resistance has been realized and that fuel efficiency is excellent.
In addition, since the low temperature tan δ was high, the wet skid resistance was good, and it was found that the balance between low fuel consumption and wet skid resistance was good.
In addition, the wear resistance was greatly improved and the tensile strength was good.
From the above, it was found that the modified conjugated diene polymer of the present invention has a performance balance that surpasses polymers obtained by known techniques.

  The modified conjugated diene polymer composition obtained by combining the modified conjugated diene polymer of the present invention with an inorganic filler is used for automobile interior / exterior products, anti-vibration rubber, belts, footwear, foams, various industrial parts, tires. There is industrial applicability in fields such as applications.

Claims (8)

Polymerizing a conjugated diene compound or a conjugated diene compound with a polyfunctional anionic polymerization initiator having a molecular weight distribution measured using gel permeation chromatography (GPC) in the range of 1.2 to 3.5 Obtaining a conjugated diene polymer obtained by copolymerizing with an aromatic vinyl compound;
At the polymerization active terminal of the conjugated diene polymer,
(I) a step in which the total number of alkoxy groups bonded to the silyl group is 4 or more and the modifier (A) having one or more nitrogen atoms is reacted;
(II) a step of reacting a modifying agent (B) in which the total number of alkoxy groups bonded to the silyl group is 2 or 3, and having one or more nitrogen atoms;
Having
A method for producing a modified conjugated diene polymer. The polyfunctional anionic polymerization initiator is
A polyfunctional anionic polymerization initiator prepared in a hydrocarbon solvent with a polyvinyl aromatic compound and an organolithium compound in a molar ratio of polyvinyl aromatic compound / organolithium compound of 0.01 to 1.0. The method for producing a modified conjugated diene polymer according to claim 1. The total number of alkoxy groups bonded to the silyl group is 4 or more, and the modifier (A) having one or more nitrogen atoms,
The method for producing a modified conjugated diene polymer according to claim 1 or 2, which is a compound represented by the following general formula (1) or general formula (2).
(In General Formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ represent an alkylene group having 1 to 20 carbon atoms. M is an integer of 1 or 2, and n is an integer of 2 or 3. In the compound represented by the general formula (1), the total number of alkoxy groups having 1 to 20 carbon atoms is 4. That's it.)
(In General Formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ represent an alkylene group having 1 to 20 carbon atoms. And when a plurality of R ⁸ , R ⁹ and A ¹ are present, they may be the same or different, and m and n are each an integer of 0 to 3.
p is an integer of 0 to 20, and when p is 2 or more, the plurality of repeating units represented by (R ⁹ -A ¹ -R ⁸ ) may be different from each other. In the compound represented by the general formula (2), the total number of alkoxy groups having 1 to 20 carbon atoms is 4 or more. A ¹ is represented by the following general formula (
It is a group represented by any one of a), (b), and (c). )
(In the general formula (a), R ¹⁰ and R ¹¹ are alkylene groups having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)
(In the general formula (b), R ⁷ is an alkyl or aryl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, and 3 organic substituted silyls. Any one selected from the group consisting of groups.)
(In the general formula (c), R ¹⁰ is an alkylene group having 1 to 20 carbon atoms, R ⁵ and R ⁶ is an alkyl group or an aryl group having 1 to 20 carbon atoms .r is an integer of 0 to 3 is there.) The total number of alkoxy groups bonded to the silyl group is 2 or 3, and the modifier (B) having one or more nitrogen atoms,
Any one selected from the group consisting of compounds represented by the following general formula (3), general formula (4), general formula (5), general formula (6), general formula (7), and general formula (8). The manufacturing method of the modified conjugated diene polymer as described in any one of Claims 1 thru | or 3.
(In the general formula ^{(3), R 1, R} 2 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ^8, R ⁹ represents an alkylene group having 1 to 20 carbon atoms , R ¹² , R ¹³ , R ¹⁴ are Si
, O, or N, and optionally substituted with an organic group having no active hydrogen.
It is a hydrocarbon group. i is an integer of 2 or 3. )
(In General Formula (4), R ¹ and R ² are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, R ⁹ is an alkylene group having 1 to 20 carbon atoms, R ¹⁰ , R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms and has a ring structure of 5 or more members with two adjacent N atoms, and R ¹⁵ has no hydrocarbon group having 1 to 20 carbon atoms and active hydrogen. 1 to 20 carbon atoms substituted with a heteroatom
And m is an integer of 2 or 3. )
(In General Formula (5), R ¹ and R ² are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, R ⁹ is an alkylene group having 1 to 20 carbon atoms, R ¹⁰ , R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms and forms a ring structure of 5 or more members with two adjacent Ns, and R ¹⁵ and R ¹⁶ are hydrocarbon groups having 1 to 20 carbon atoms, active hydrogen Carbon atoms substituted with hetero atoms having no carbon atom
-20 hydrocarbon groups or 3 organic substituted silyl groups, m is an integer of 2 or 3. )
(In General Formula (6), A ² is a monovalent group having at least one functional group selected from tertiary amine, pyridine, cyan, and imine, and R ¹ and R ² are each independently And an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁸ is an alkylene group having 1 to 20 carbon atoms, and m is an integer of 2 or 3.)
In (formula ^{(7), R 1, R} 2, R 6 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁸ represents an alkylene group having 1 to 20 carbon atoms .
R ³ , R ⁴ and R ⁵ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms,
Or two of them may be bonded together to form a ring together with the silicon atoms to which they are bonded. m is an integer of 1 to 2, and f is an integer of 1 to 10. )
In (formula ^{(8), R 1, R} 2 are each independently, represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁸ is .R ³ representing an alkylene group having 1 to 20 carbon atoms , R ⁴ and R ⁵ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other to form a ring together with the silicon atom to which they are bonded. May be formed.) Molecular weight distribution measured using gel permeation chromatography (GPC)
Using a polyfunctional anionic polymerization initiator having a molecular weight of 1.2 to 3.5,
Polymerization or copolymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer;
At the polymerization active terminal of the conjugated diene polymer,
( I) The total number of alkoxy groups bonded to the silyl group is 4 or more, and one or more nitrogen atoms
Reacting the modifier (A) with
(II) The total number of alkoxy groups bonded to the silyl group is 2 or 3, and one or more nitrogen
Reacting the modifying agent (B) having an atom
A step of producing a modified conjugated diene polymer,
A step of mixing the silica-based inorganic filler from 0.5 to 300 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer,
A process for producing a modified conjugated diene polymer composition. For 100 parts by mass of the rubber component containing 20 parts by mass or more of the modified conjugated diene polymer,
The method for producing a modified conjugated diene polymer composition according to claim 5 , further comprising mixing 0.5 to 100 parts by mass of carbon black. Molecular weight distribution measured using gel permeation chromatography (GPC)
Using a polyfunctional anionic polymerization initiator having a molecular weight of 1.2 to 3.5,
Polymerization or copolymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer;
At the polymerization active terminal of the conjugated diene polymer,
( I) The total number of alkoxy groups bonded to the silyl group is 4 or more, and one or more nitrogen atoms
Reacting the modifier (A) with
(II) The total number of alkoxy groups bonded to the silyl group is 2 or 3, and one or more nitrogen
Reacting the modifying agent (B) having an atom
A step of producing a modified conjugated diene polymer,
Mixing 0.5 to 300 parts by mass of a silica-based inorganic filler with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer, and producing a modified conjugated diene polymer composition;
Molding using the modified conjugated diene polymer composition;
Having
A method for producing a tire comprising a modified conjugated diene polymer composition. Molecular weight distribution measured using gel permeation chromatography (GPC)
Using a polyfunctional anionic polymerization initiator having a molecular weight of 1.2 to 3.5,
Polymerization or copolymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer;
At the polymerization active terminal of the conjugated diene polymer,
( I) The total number of alkoxy groups bonded to the silyl group is 4 or more, and one or more nitrogen atoms
Reacting the modifier (A) with
(II) The total number of alkoxy groups bonded to the silyl group is 2 or 3, and one or more nitrogen
Reacting the modifying agent (B) having an atom
A step of producing a modified conjugated diene polymer,
The rubber component 100 containing 0.5 to 300 parts by mass of a silica-based inorganic filler with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer, and containing 20 parts by mass or more of the modified conjugated diene polymer. A step of producing a modified conjugated diene polymer composition by a step of further mixing 0.5 to 100 parts by mass of carbon black with respect to parts by mass;
Having a step of molding using the modified conjugated diene polymer composition,
A method for producing a tire comprising a modified conjugated diene polymer composition.