JP3441201B2 - Polymer and polymer composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer and a polymer composition thereof, and more particularly to a novel polymer having excellent breaking properties, abrasion resistance and low hysteresis loss (low rolling resistance, low fuel consumption). The present invention relates to a polymer and a polymer composition for a tire tread using this polymer.

[0002]

2. Description of the Related Art In recent years, as tires have been improved in performance, rubbers for tire treads which are excellent in fracture characteristics, wear resistance and low hysteresis loss (low rolling resistance) have been demanded.

To reduce the hysteresis loss, cis-1,4-polybutadiene rubber or the like is used. Although it has good wear resistance, it has poor fracture characteristics. A solution having a significantly improved low hysteresis loss property is a solution-polymerized butadiene-styrene rubber having a tin-carbon bond in the molecular chain, which is used in a rubber composition of a fuel-efficient tire tread, but has a wet grip. And balance between low rolling resistance and low rolling resistance are not always good.

Even a tread rubber composition using such a rubber and carbon black alone as a filler can balance various physical properties and performances to some extent, but has a wet grip property and a low property which are rapidly increasing in recent years. It is difficult to meet the needs for a higher degree of compatibility with rolling resistance. In order to solve this problem, a rubber composition is known in which carbon black and white carbon such as silica are used together as a filler or only white carbon is used.

For example, a rubber composition containing a polymer having a polymer terminal modified with a silane compound and silica (for example, Japanese Examined Patent Publication 5).
2-5071, JP-A-56-104906, JP-A-62-50346, and JP-A-62-227908). However, in these polymers, the residual amount of the alkoxy group is not sufficient and the obtained polymer is a one-end modified polymer, and therefore, the reinforcing property and the dispersion improving effect on the filler such as silica, and the mechanical property. The effect of improving physical properties is not sufficient. In addition, even if dilithium is used as an initiator in such a polymer (JP-A-62-2).
No. 27908), both ends are modified with an alkoxysilane, which has a coupling ability, which makes it difficult to control the molecular weight, and the viscosity of the polymer cement before and after modification becomes high, resulting in steam strip resistance and aging of the bulk polymer produced. Also causes problems.

Further, a rubber composition containing a polymer having a polymer terminal modified with a nitrogen-containing compound and silica (for example, JP-A-64-22940) is also known. This is a diene-based polymer obtained by initiating polymerization with alkyllithium, but mainly uses a polymer obtained by copolymerizing a monomer containing a nitrogen atom at the terminal end of the polymerization or by terminal modification with an aminobenzophenone compound. , Is a one-end modification with a compound containing a nitrogen atom as described above,
Reinforcing property against silica etc. is insufficient.

Further, a rubber composition (pneumatic tire) containing solution-polymerized butadiene-styrene rubber having a specific molecular structure and silica (for example, JP-A-3-239737) is also provided. This provides some improvement in silica reinforcement, but is not sufficient.

Moreover, a diene polymer is mainly used for these polymers. It is known that a diene polymer has a low affinity for white carbon such as silica, and it is difficult to obtain a uniformly dispersed rubber composition by kneading. To compensate for this, in many cases, expensive silane coupling agents are blended in large amounts. Since this silane coupling agent is easily hydrolyzed in the air, it requires careful handling and it is difficult to obtain a rubber composition with good reproducibility.

Therefore, the above-mentioned various rubber compositions essentially contain the diene polymer as silica even if the silane coupling agent is sufficiently controlled and used, and even when the silane coupling agent is not used. Insufficient affinity and dispersibility with silica, it is difficult to obtain the reinforcing effect of silica, and it does not show sufficient fracture characteristics, and various physical properties such as abrasion resistance, wet grip property, low rolling resistance, etc. Is difficult to balance at a high level.

[0010]

As described above, at present, a polymer composition which satisfies various required characteristics in a well-balanced manner and has practicality has not yet been obtained.

The present invention provides a novel polymer excellent in fracture characteristics, abrasion resistance and low hysteresis loss (low rolling resistance, low fuel consumption), and a polymer composition using this polymer. Has an aim.

[0012]

The polymer of the present invention comprises a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer having a functional group containing a nitrogen atom bonded to the terminal portion thereof, and the polymer is separated from the conjugated diene polymer or the copolymer. At least one of the molecular structures represented by the following general formula (I), in which a functional group having a hydroxyl group is bonded to the moiety and a silicon having at least one alkoxy group is bonded to the functional group. It is characterized by consisting of two.

[0013]

[Chemical 5]

(In the formula, P represents a polymer or a copolymer, and R ¹ , R ² , R ⁶ and R ⁷ are selected from aliphatic, alicyclic and aromatic hydrocarbon groups having 1 to 20 carbon atoms. represents a group, or different, even the same, R ³ is an aliphatic having 1 to 20 carbon atoms, represents a group selected from the hydrocarbon groups alicyclic, R ⁴ is an oxygen atom, a methylene group Or a methylene group having a substituent, R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of OR ⁶ groups, R ⁶ may be the same or different. ¹ and R ² may combine with each other to form a cyclic structure containing the nitrogen atom, or a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure. Ok x
Is an integer of 1 to 3, y is an integer of 1 to 3, z is 0 or 1 or 2.
, And x + y + z represents an integer of 2-4. n is 0
Or represents 1. )

Further, another polymer of the present invention has a hydrogen atom bonded to a terminal portion of a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer, and has a hydroxyl group in another portion of the polymer or the copolymer. The following general formula (II), in which a functional group is bound and silicon having at least one oxy group is bound to the functional group
It is characterized by comprising at least one of the molecular structures represented by.

[0016]

[Chemical 6]

(In the formula, P represents a polymer or a copolymer, R ³ represents a group selected from aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, and R ⁴ represents an oxygen atom or a methylene group. Or a methylene group having a substituent, R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ each represent an aliphatic, alicyclic, or aromatic group having 1 to 20 carbon atoms. Represents a group selected from hydrocarbon groups, which may be the same or different.When there are a plurality of OR ⁶ groups, R ⁶ may be the same or different, and x is an integer of 1 to 3. , Y is an integer of 1 to 3, z is 0 or an integer of 1 to 2, and x + y + z is 2
Represents an integer of 4. n represents 0 or 1. )

The polymer composition of the present invention comprises a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer having a nitrogen atom-containing functional group bonded to the terminal portion thereof and a hydroxyl group at another portion of the polymer or copolymer. A polymer comprising at least one of the molecular structures represented by the following general formula (I), wherein the polymer has a functional group having a bond with and a silicon having at least one alkoxy group is bonded to the functional group. 100 parts by weight of a rubber raw material containing 10 parts by weight or more and 10 to 100 parts by weight of a filler containing white carbon.

[0019]

[Chemical 7]

(In the formula, P represents a polymer or a copolymer, and R ¹ , R ² , R ⁶ and R ⁷ are selected from aliphatic, alicyclic and aromatic hydrocarbon groups having 1 to 20 carbon atoms. represents a group, or different, even the same, R ³ is an aliphatic having 1 to 20 carbon atoms, represents a group selected from the hydrocarbon groups alicyclic, R ⁴ is an oxygen atom, a methylene group Or a methylene group having a substituent, R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of OR ⁶ groups, R ⁶ may be the same or different. ¹ and R ² may combine with each other to form a cyclic structure containing the nitrogen atom, or a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure. Ok x
Is an integer of 1 to 3, y is an integer of 1 to 3, z is 0 or 1 or 2.
, And x + y + z represents an integer of 2-4. n is 0
Or represents 1. )

Another polymer composition of the present invention has a hydrogen atom bonded to a terminal portion of a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer, and a hydroxyl group in another portion of the polymer or the copolymer. A polymer having at least one of the molecular structures represented by the following general formula (II), which contains a functional group and silicon having at least one alkoxy group bonded to the functional group, is provided. 100 parts by weight of a rubber raw material containing at least 1 part by weight, and 10 to 100 parts by weight of a filler containing white carbon are included.

[0022]

[Chemical 8]

(In the formula, P represents a polymer or a copolymer, R ³ represents a group selected from aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, R ⁴ represents an oxygen atom or a methylene group. Or a methylene group having a substituent, R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ each represent an aliphatic, alicyclic, or aromatic group having 1 to 20 carbon atoms. Represents a group selected from hydrocarbon groups, which may be the same or different.When there are a plurality of OR ⁶ groups, R ⁶ may be the same or different, and x is an integer of 1 to 3. , Y is an integer of 1 to 3, z is 0 or an integer of 1 to 2, and x + y + z is 2
Represents an integer of 4. n represents 0 or 1. )

The present inventor has found that the polymer constituents, fillers,
As a result of intensive investigations focusing on those physical properties and the like, as a result of, for example, a polymer having a molecular structure of butadiene-styrene random copolymer / hydroxypropylalkoxysilane and a polymer composition containing this polymer and white carbon, the present invention Found that the purpose of
The present invention has been completed.

This effect is manifested by the fact that the surface of the filler silica can react with the polymer alkoxy functional group, and at the same time, the polymer hydroxyl group near the functional group and the silanol group on the silica surface have high affinity. It is thought that it depends.
In addition to this structure, a polymer having a tertiary amine bonded to the polymer terminal in some examples can further improve this effect.

The present invention will be described in detail below. P represented by the general formulas (I) and (II) of the present invention represents a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer. A conjugated diene polymer is a polymer composed of conjugated diene units obtained by polymerizing a conjugated diene monomer. The conjugated diene monomer is a conjugated diene hydrocarbon containing 4 to 12, preferably 4 to 8 carbon atoms per molecule. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3
-Pentadiene, octadiene and the like. These may be used alone or in admixture of two or more, especially 1,3
-Butadiene is preferred.

The conjugated diene / vinyl aromatic hydrocarbon copolymer is a copolymer composed of a conjugated diene unit and a vinyl aromatic hydrocarbon unit, which is obtained by copolymerizing a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer.
Examples of the vinyl aromatic hydrocarbon monomer include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene and the like, and styrene is particularly preferable.

The conjugated diene polymer is preferably polybutadiene having excellent abrasion resistance and the like, and the conjugated diene / vinyl aromatic hydrocarbon copolymer is preferably butadiene / styrene copolymer having excellent abrasion resistance and aging resistance. The microstructure (cis-1,4, trans-1,4, vinyl) of the butadiene portion in the conjugated diene polymer such as polybutadiene and the butadiene / styrene copolymer is not particularly limited, but is usually within the range obtained by the organolithium catalyst system. Can take structure. The composition of the conjugated diene / vinyl aromatic hydrocarbon copolymer such as butadiene / styrene copolymer is not particularly limited, but a weight ratio of 30/70 to 95/5 is usually used,
The composition distribution of the copolymer may have a random structure, a block structure or an intermediate structure thereof, but a random structure or an intermediate structure is usually preferable.

Next, the structure of one end of the polymer of the present invention will be described. A functional group containing a nitrogen atom in the general formula (I) and a hydrogen atom in the general formula (II) are bonded to the terminal portion of the polymer or copolymer of the polymer of the present invention.

The functional group containing a nitrogen atom is represented by R ¹ R ² N-, and R ¹ and R ² are groups selected from aliphatic, alicyclic and aromatic hydrocarbon groups having 1 to 20 carbon atoms. Preferably, a group selected from aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbon groups having 1 to 13 carbon atoms, that is, a residue of a secondary amine compound, from the viewpoints of breaking properties and low hysteresis loss. Represent R ¹ and R ² may be bonded to each other to form a cyclic structure containing the nitrogen atom, or a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure. It means that the residue of the imine compound may be formed well. In this case, R ¹ and R
² is a group selected from saturated or unsaturated cyclic hydrocarbon machines containing the nitrogen atom having 2 to 20 carbon atoms formed by bonding to each other, that is, imine compound residue, preferably, breaking property and low hysteresis loss property From the viewpoint of
Represents a group selected from 13 imine compound residues. In order to further improve physical properties such as breaking properties and low hysteresis loss, R ¹ and R ² are preferably a cyclic structure formed by bonding, that is, a residue of an imine compound.

Examples of the secondary amine compound include dimethylamine, diethylamine, dipropylamine, di-n-butylamine, diisobutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, diallylamine, dicyclohexylamine, butylisopropyl. Examples thereof include amine, dibenzylamine, methylbenzylamine, methylhexylamine, ethylhexylamine and the like. Among them, it is preferable that R ¹ and R ² are amines each having a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms, because the breaking property and the low hysteresis loss property can be further improved.

Examples of the imine compound include aziridine, azetidine, pyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine and hepta. Methyleneimine, coniine, morpholine, N-methylpiperazine, N
-Methylpiperazine, N-ethylpiperazine, N-methylimidazolidine, N-ethylimidazolidine, oxazine, pyrroline, pyrrole, azepine and the like can be exemplified. Among them, a group selected from imine compound residues having 4 to 12 carbon atoms is preferable because the breaking property and the low hysteresis loss property can be further improved.

R ³ in the general formula (I) and the general formula (II) represents a group selected from aliphatic and alicyclic hydrocarbon groups having 1 to 20 carbon atoms, and has a breaking property and A group selected from aliphatic and alicyclic hydrocarbon groups having 1 to 6 carbon atoms is preferable in order to further improve the low hysteresis loss property.

Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Examples thereof include a group such as octyl, and a methyl group, an ethyl group and a propyl group, which can further improve the effects of the present invention, are preferable. As the alicyclic hydrocarbon group,
Examples thereof include groups such as cyclopentyl, cyclohexyl and cycloheptyl, and a cyclohexyl group that can further improve the effects of the present invention is preferable.

R ⁴ in the general formulas (I) and (II) is an oxygen atom, a methylene group or a methylene group having a substituent, and the substituent is, for example, methyl, ethyl, propyl or the like. The following groups can be mentioned. R ⁴ is preferably an oxygen atom or a methylene group from the viewpoint of breaking properties and low hysteresis loss.

R ⁵ in the general formulas (I) and (II) represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms,
Aliphatic hydrocarbon groups having 1 to 10 carbon atoms are preferable, and examples thereof include groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups. Among them, preferred are fracture characteristics and low hysteresis loss. To a methyl group, an ethyl group, a propyl group, and a butyl group.

R ⁶ and R ⁷ represented by the general formula (I) and the general formula (II) are each an aliphatic or alicyclic group having 1 to 20 carbon atoms,
Represents a group selected from each aromatic hydrocarbon group, the aliphatic hydrocarbon group and alicyclic hydrocarbon group have the same meaning as the above R ³ , and in particular, the number of carbon atoms is 1 to 1 from the viewpoint of reactivity with the silica surface.
Alkyl groups of 3 are preferred. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthryl, and phenanthryl groups, with the phenyl group being preferred. R ⁶ is even more preferably
It represents a group selected from methyl, ethyl, propyl, and phenyl groups, which can further improve the breaking property and the low hysteresis loss property. R ⁷ is OR ⁶ bonded to silicon in the polymer and, depending on the number of the polymer or the copolymer (in the general formula (I) and the general formula (II),
x + y + z = 4), not present in the polymer.

In the general formulas (I) and (II), x is an integer of 1 to 3, y is an integer of 1 to 3, z is 0 or 1.
Is an integer of 2 and x + y + z is an integer of 2-4. x
When 1 is 1, y is 1 to 3, when x is 2, y is 1 to 2, and when x is 3, y is 1. Therefore, in each case,
It is determined whether z is 0 to 2. The polymer of the present invention will be described later in the production method, depending on the production conditions,
x, y, and z can vary within a range that satisfies the above conditions, and are not particularly limited. In some cases, x, y, and z are fixed and are one polymer, and in other cases, x, y, and z are a mixture of a plurality of different polymers. Usually, it is often the latter mixture.

N in the general formulas (I) and (II) represents 0 or 1. _{^{Therefore,> R 3 - (CH 2}} ) n -
OH represents one of> R ³ —CH ₂ —OH and> R ³ —OH. When R ³ is an aliphatic hydrocarbon group, n is either 0 or 1 or a mixture,
When R ³ is an alicyclic hydrocarbon group, n is 0, and>
It has a structure of only R ³ —OH.

The polymer represented by the general formula (I) or the general formula (II) is a combination of the above-mentioned molecular structural elements. In order to further improve various physical properties, a polymer composition is prepared. In this case, in order to remarkably improve the interaction with silica described later, R ¹ and R ² each have a carbon number of 1 to
A group selected from 13 aliphatic, alicyclic, and aromatic hydrocarbon groups, or 2 to 1 carbon atoms formed by bonding to each other.
A group selected from an imine compound residue containing 3 nitrogen atoms, and a group selected from the hydrocarbon groups aliphatic having 1 to 6 carbon atoms and alicyclic as R ^3, an oxygen atom or a methylene group as R ⁴ A group selected from aliphatic hydrocarbon groups having 1 to 4 carbon atoms as R ⁵ , a group selected from aliphatic and aromatic hydrocarbon groups having 1 to ⁶ carbon atoms as R ⁶ , and R ⁷ A polymer having an aliphatic hydrocarbon group having 1 to 3 carbon atoms and a group selected from a phenyl group, and a hydrogen atom at the terminal of the polymer, and an aliphatic or alicyclic group having 1 to 6 carbon atoms as R ³ . A group selected from each hydrocarbon group, an oxygen atom or a methylene group as R ⁴ , a group selected from an aliphatic hydrocarbon group having 1 to 4 carbon atoms as R ⁵ , and a fat having 1 to ⁶ carbon atoms as R ^6. A group selected from each group of aromatic and aromatic hydrocarbon groups;
A polymer having ⁷ as an aliphatic hydrocarbon group having 1 to 3 carbon atoms and a group selected from a phenyl group is preferable.

Preferred examples of such preferred polymers include those shown in the following table.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

R ⁷ in the table may or may not be present in the polymer as described above, and examples thereof are shown.

The molecular structure of the polymer will be shown in the following example of the method for producing the polymer. The method for producing the polymer of the present invention is not particularly limited, but the production method is illustrated below.

Among the polymers of the present invention, the polymer represented by the general formula (I) having a nitrogen atom at the terminal and the polymer represented by the general formula (II) having hydrogen at the terminal. The difference from the case of producing a polymer having atoms is only whether or not the step of introducing a nitrogen atom is provided.

In order to obtain the polymer represented by the general formula (I), a lithium amide initiator obtained from a secondary amine compound such as diethylamine or an imine compound such as hexamethyleneimine and an organic lithium compound is used. It can be obtained by adding a monomer to start the polymerization of the monomer and then adding a silane compound having an epoxy group or a glycidoxy group to the polymer solution having a lithium active terminal.

The polymer represented by the general formula (I) is
In addition to the above method, a secondary amine compound or an imine compound is added in the presence of at least a monomer to advance the polymerization of a monomer using a lithium amide catalyst as an initiator, and then to the polymer solution having a lithium active terminal. It can be obtained by adding a silane compound having an epoxy group or a glycidoxy group. That is, in the method for producing the polymer represented by the general formula (I), the same procedure is performed by using only the organolithium compound (eg, butyllithium) without using the secondary amine compound or the imine compound (eg, HMI). A polymer represented by the general formula (II) can be obtained through the step of.

Here, among the polymers of the present invention, the polymer represented by the general formula (I), which is produced by the latter method, contains butadiene (B) and styrene (S) as monomers. (The copolymer is BSP), hexamethyleneimine (HMI) is used as the imine compound, and 3-glycidoxypropyltrimethoxysilane (GPMOS) is used as the silane compound having an epoxy group, to obtain the polymer of the present invention. A production example is shown in A. The resulting polymer becomes A-1, A-2 and / or A-3. A production example similar to A is shown in B except that β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (EHMOS) is used instead of GPMOS. The obtained polymer is B-
1, B-2 and / or B-3.

[0053]

[Chemical 9]

[0054]

[Chemical 10]

The --CH ₂ --CH (OH)-CH ₂ --structure in A-1, A-2 and A-3 of this Production Example is --CH.
In some cases, the structure may be (CH ₂ —OH) —CH ₂ —,
It may have both structures.

The secondary amine compound or imine compound used in this production method is as described above.

As the silane compound having an epoxy group, for example, 3-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxybutyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropyltriphenoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Propoxysilane, 3-glycidoxypropylmethyldibutoxysilane, 3-glycidoxypropylmethyldiphenoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 3-glycidyl Doxypropyldimethylethoxysilane, 3-glycidoxypropyldimethylphenoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropylmethyldiisopropeneoxysilane, bis (3-glycidoxypropyl) dimethoxy Silane, bis (3-glycidoxypropyl) diethoxysilane, bis (3-glycidoxypropyl) dipropoxysilane, bis (3-glycidoxypropyl) dibutoxysilane, bis (3-glycidoxypropyl) Diphenoxysilane, bis (3-glycidoxypropyl) methylmethoxysilane, bis (3-glycidoxypropyl) methylethoxysilane, bis (3-glycidoxypropyl) methylpropoxysilane, bis (3-glycidoxy) Propyl) methylbutoxysilane Bis (3-glycidoxypropyl) methylphenoxy silane, tris (3-glycidoxypropyl) methoxysilane, beta-
(3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β-
(3,4-Epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl)
Ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane,
β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β
-(3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane and the like can be mentioned. Of these, 3-glycidoxypropyltrimethoxysilane is preferable because it further improves physical properties such as abrasion resistance and low hysteresis loss.

In this production method, examples of the solvent used as the polymerization solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-butane. Aliphatic hydrocarbon solvents such as methylcyclopentane and cyclohexane, and mixtures thereof can be used without particular limitation.

The lithium compound as the polymerization initiator used in this production method includes alkyllithium such as n-butyllithium, ethyllithium, propyllithium, t-butyllithium and hexyllithium, and alkylenediamine such as 1,4-dilithiobutane. Lithium, phenyllithium,
Other hydrocarbon lithium such as stilbendilithium, a reaction product of butyllithium and divinylbenzene, or organometallic lithium such as tributyltin lithium, lithium hexamerenimide, lithium diethylamide, lithium amide such as lithium pyrrolidide can be mentioned. . These lithium initiators may be used alone or in combination of two or more. In the case of the polymer of the general formula (I), for example, when alkyl lithium is used in combination with a secondary amine compound or an imine compound in the polymerization system as an initiator, n-butyl lithium or sec- Butyl lithium and the like are preferable from the viewpoint of solubility and initiation rate in a hydrocarbon solvent, on the other hand, when a lithium amide-based initiator is used from the beginning, lithium hexamethylene imide, lithium pyrrolidide, lithium diethyl amide and the like are used. From the viewpoints of solubility in hydrocarbon solvents and reinforcement of white carbon such as silica. The amount of these lithium compounds used can be in the range of 0.2 to 30 mmol per 100 g of the monomer. If it is less than 0.2 mmol or more than 30 mmol, it is not preferable from the viewpoint of processability of the obtained polymer.

The conjugated diene monomer or vinyl aromatic hydrocarbon monomer used for the polymerization is as described above.

In this polymerization, a randomizer is preferably used when it is desired to obtain a polymer having a desired molecular structure. The randomizer referred to herein means control of the microstructure of the conjugated diene polymer, for example, increase of 1,2 bond of butadiene portion of butadiene polymer or butadiene-styrene copolymer, increase of 3,4 bond of isoprene polymer and the like. Control of composition distribution of monomer units of conjugated diene-vinyl aromatic hydrocarbon copolymer, for example, butadiene-
It is a compound having a function of randomizing butadiene units and styrene units of a styrene copolymer. The randomizer according to the present invention is not particularly limited, but includes all commonly used randomizers. Examples of the randomizer used include the following. (1) Ethers (2) Ortho-dimethoxybenzenes (3) Complex of alkali metal and ketone or phosphite triester (4) Compound R (OM ¹ ) _n , (RO) ₂ represented by the following general formula M ² , R (COOM ¹ ) _n , RO
COOM ¹ , RSO ₃ M ¹ , ROSO ₃ M ¹ (wherein R is selected from aliphatic, alicyclic and aromatic hydrocarbon groups, M ¹ is an alkali metal,
In particular, it represents lithium, sodium, potassium, rubidium or cesium, M ² is an alkaline earth metal, specifically calcium or barium, and n is from 1 to 1.
It is an integer of 3. (5) Tertiary amine or less The randomizer will be specifically described, but these randomizers may be used alone or in combination.

(1) Examples of ethers include 1,2-
Examples thereof include dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methoxymethyltetrahydrofuran, diethyl ether, triethylene glycol dimethyl ether and the like.

(2) Examples of orthodimethoxybenzenes include veratrol, isohomoveratrol and the like.

(3) Complexes of alkali metal with ketone or phosphite triester include ketones such as acetone, methyl ethyl ketone, diisopropyl ketone, benzophenone, acetophenone, dibenzyl ketone, fluorenone, xanthone, Michler's ketone and acetylacetone. Phosphite triesters such as triethyl phosphite, trioctyl phosphite, tribenzyl phosphite and trinonyl phosphite,
Examples thereof include complexes with lithium, sodium, potassium, rubidium or cesium.

(4) The randomizer represented by the general formula will be described. Specific examples of the alcohol represented by the general formula R (OM ¹ ) _n or (RO) ₂ M ² and the alkali metal salt or alkaline earth metal salt of phenol include methyl alcohol, ethyl alcohol, isopropyl alcohol, tert.
-Butyl alcohol, tert-amyl alcohol, cyclohexyl alcohol, allyl alcohol, 2-butenyl alcohol, benzyl alcohol, phenol, catechol, resorcinol, hydroquinone, 1-naphthyl alcohol, p-nonylphenol, pyrogallol, etc. lithium, sodium, potassium, Rubidium, cesium, calcium and barium salts are included.

The general formula R (COOM ¹ ) _n or ROCOOM
Specific examples of the alkali metal carboxylic acid and acidic carbonic acid ester salt represented by ¹ , are isovaleric acid, lauric acid,
Palmitic acid, stearic acid, oleic acid, rosin acid,
Examples thereof include lithium, sodium, potassium, rubidium and cesium salts such as benzoic acid, pimelic acid, acidic n-dodecyl carbonate and acidic phenyl carbonate.

Specific examples of the alkali metal sulfonic acid and sulfate ester salt represented by the general formula RSO ₃ M ¹ or ROSO ₃ M ¹ include dodecylbenzene sulfonic acid,
Diisopropylnaphthalenesulfonic acid, N-methyl-N
Includes lithium, sodium, potassium, rubidium and cesium salts such as methane sulfonate lauryl amide, sulfate salt of lauryl alcohol, caproyl ethylene glycol sulfate ester.

(5) Examples of tertiary amines include triethylamine and tetramethylethylenediamine.

Among these, preferable randomizers include the above-mentioned (1) ethers and (4) R (OM ¹ ) _{n, which} are particularly easy to control the molecular structure of the polymer of the present invention.

The randomizer is used in an amount of 0.01 to 1000 molar equivalents per 1 molar equivalent of the organolithium compound.

The polymerization temperature is usually from -20 to 150 ° C,
It is preferably 0 to 100 ° C. The monomer concentration in the solvent is usually 5 to 50% by weight, preferably 10 to 3%.
It is 5% by weight. In the case of copolymerization of conjugated diene and vinyl aromatic hydrocarbon, the content of vinyl aromatic hydrocarbon in the charged monomer mixture is 5 to 70% by weight, preferably 10 to 5% by weight.
It is 0% by weight.

The polymerization reaction is carried out by contacting the monomer in the liquid phase with the catalyst, but it is usually preferred to operate at a pressure sufficient to maintain the liquid phase in nature.
In addition, it is preferable to exclude substances interfering with the catalytic action from all the above substances charged into the reaction system. The reaction carried out by adding a silane compound having an epoxy group after the polymerization is carried out in an atmosphere that does not deactivate the active terminal lithium of the polymer or copolymer.

After completion of the reaction, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to coagulate the polymer, followed by drying on a hot roll or under reduced pressure. Can be obtained. Alternatively, the polymer can be obtained by directly removing the solvent from the polymer solution on a hot roll or under reduced pressure.

As the rubber raw material of the polymer of the present invention, the above-mentioned polymer is blended with natural rubber or other synthetic rubber in practical use. In the case of blending, it is necessary to include 10 parts by weight or more of the polymer in 100 parts by weight of the rubber raw material, and preferably 40 parts by weight or more in order to fully exert the effect of the polymer of the present invention. . For example, in a blend with natural rubber, if the amount of the polymer used in the present invention is less than 10% by weight, the balance of the properties required for the polymer composition is impaired, which is not preferable.

Examples of the synthetic rubber to be blended and used include cis-1,4-polyisoprene, styrene-butadiene copolymer, low cis-1,4-polybutadiene, high cis-1,4-polybutadiene, ethylene- Examples thereof include propylene-diene copolymer, chloroprene, halogenated butyl rubber, acrylonitrile-butadiene rubber (NBR) and the like. Of these, natural rubber, high cis-1,4-polybutadiene, and halogenated butyl rubber are preferable from the viewpoint of tensile strength, wear resistance, and workability.

The polymer composition of the present invention contains a filler, and white carbon is an essential component in this filler.

The white carbon used in the polymer composition of the present invention includes, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, clay, talc, calcium carbonate, Contains basic magnesium carbonate, alumina hydrate, diatomaceous earth, barium sulfate, mica, alumina sulfate, titanium oxide, etc.,
Among them, wet silica is preferable because it has the most remarkable effect of improving the fracture characteristics and the effect of simultaneously achieving both wet grip properties and low rolling resistance.

The compounding amount of the filler is 10 to 100 parts by weight with respect to 100 parts by weight of the rubber raw material, and from the viewpoint of the reinforcing property by the white carbon contained in the filler and the efficiency of improving various physical properties by it, It is preferably 20 to 60 parts by weight. If the amount is less than 10 parts by weight, the breaking properties are not sufficient,
Further, if it exceeds 100 parts by weight, the workability is deteriorated.

The filler of the present invention can be only white carbon. In this case, the white carbon is used in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the rubber raw material, and is preferably 20 to 60 parts by weight from the viewpoint of the reinforcing property and the effect of improving various physical properties. When the amount is less than 10 parts by weight, the fracture characteristics and the like are insufficient, and when the amount exceeds 100 parts by weight, the workability is deteriorated.

The filler used in the polymer composition of the present invention may be white carbon or carbon black. As a result, the effect of improving various physical properties becomes greater. As the carbon black used, FE
Carbon black such as F, SRF, HAF, ISAF, and SAF, preferably having an iodine adsorption amount (IA) of 60.
mg / g or more and dibutyl phthalate oil absorption (DB
Carbon black having P) of 80 ml / 100 g or more is used. Especially, HAF, ISAF, which has excellent wear resistance,
SAF is preferred. The blending amount of carbon black is not particularly limited as long as it does not impair the action and effect of white carbon, but from the viewpoint of reinforcing properties and processability, within the range of the filler with respect to 100 parts by weight of the raw rubber. , 0.1 to 90 parts by weight of carbon black and 9.9 to
It is preferable to mix 99.9 parts by weight of white carbon.

In the polymer composition of the present invention, a silane coupling agent can be used at the time of compounding in order to further improve the reinforcing property of white carbon. The silane coupling agent is exemplified as follows. .

Bis (3-triethoxysilylpropyl)
Tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-
Nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2
-Chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2 -Triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3- Examples thereof include trimethoxysilylpropyl methacrylate monosulfide, bis (3-triethoxysilylpropyl) tetrasulfide, 3-trimethoxysilylpropyl benzo. Azole tetrasulfide and the like,
It is preferable from the viewpoint of reinforcing effect. In addition, as another example, bis (3-diethoxymethylsilylpropyl)
Tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazoletetrasulfide Is mentioned.

When a silane coupling agent is used in the polymer composition at the time of compounding, the amount thereof added can be reduced from the usual amount while maintaining the same physical properties, and varies depending on the amount of white carbon compounded. However, from the viewpoint of reinforcement, the amount is 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the rubber raw material.

Examples of the vulcanizing agent include sulfur and the like. The amount of these is 0.1 to 100 parts by weight of the rubber raw material.
5 parts by weight, preferably 1-2 parts by weight. If the amount is less than 0.1 parts by weight, the breaking strength, wear resistance and hysteresis loss of the vulcanized rubber will be reduced, and if it exceeds 5 parts by weight, the rubber elasticity will be lost.

Examples of process oils that can be used in the polymer composition of the present invention include paraffinic oils, naphthene oils, aromatic oils and the like. An aromatic type is used for applications where importance is attached to tensile strength and wear resistance, and a naphthene type or paraffin type is used for applications where importance is attached to hysteresis loss and low temperature characteristics. The amount of use is 100 parts by weight of rubber raw material. It is from 0 to 100 parts by weight, and if it exceeds 100 parts by weight, the tensile strength and low hysteresis loss of the vulcanized rubber are significantly deteriorated.

The vulcanization accelerator which can be used in the present invention is not particularly limited, but preferably M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2). -Benzothiazylsulfenamide) and other thiazole-based DPGs
Examples of the vulcanization accelerator include a guadinine-based vulcanization accelerator such as (diphenylguanidine).
0.1 to 5 parts by weight, preferably 0.2
~ 3 parts by weight.

In the present invention, in addition to these, additives such as an antioxidant, zinc oxide, stearic acid, an antioxidant and an antiozonant which are commonly used in the rubber industry can be blended.

The polymer composition of the present invention is obtained by kneading using a kneading machine such as a roll or an internal mixer. After molding, vulcanization is performed to obtain a tire tread, an undertread, a carcass, It can be used not only for tires such as sidewalls and beads, but also for applications such as anti-vibration rubber, belts, hoses and other industrial products.
Particularly, it is preferably used as rubber for tire tread.

[0089]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

In the examples, parts and% mean parts by weight and% by weight, unless otherwise specified.

Various measurements were made by the following methods. Number average molecular weight (Mn) and weight average molecular weight (M
w) is measured by gel permeation chromatography [GPC; Tosoh HLC-8020, column; Tosoh GMH-XL (two in series)], and monodisperse polystyrene is standardized using a differential refractive index (RI). Was calculated in terms of polystyrene.

The microstructure of the butadiene portion of the polymer was determined by the infrared method (Morero method). The bound styrene content of the butadiene-styrene copolymer is ¹ H-
It was calculated from the integration ratio of the NMR spectrum.

Compound Mooney (ML _{1 + 4} ) is JI
It was measured at 130 ° C. according to SK6300.

As an index of hysteresis loss property, tan δ
Was used. It is evaluated that the smaller tan δ is, the lower the hysteresis loss property is. The tan δ was measured using a viscoelasticity measuring device (manufactured by Rheometrics) at a temperature of 50 ° C., strain of 8% and frequency of 15 Hz.

Fracture characteristics and 300% modulus (M
₃₀₀ ) was measured according to JIS K6301. The wear resistance was measured by using a Lambourn type wear tester and measuring the wear amount at a slip ratio of 60% at room temperature. The abrasion resistance index was expressed by indexing the abrasion resistance of the HAF carbon 50 parts blend of the same kind as 100 and others.

Example 1 Dried and nitrogen-substituted 80
In a 0 ml pressure-resistant glass container, according to the formulation of Table 6, 315 g of cyclohexane and 48 of 1,3-butadiene monomer
g, styrene monomer 12 g, tetrahydrofuran (T
After injecting 27.5 mmol of HF) and adding 0.5 mmol of n-butyllithium (BuLi) thereto, 50 ° C.
Was polymerized for 2 hours. The polymerization conversion rate was almost 100%. A portion of the copolymer was sampled, isopropyl alcohol was added, and the solid was dried to obtain a rubbery copolymer. The microstructure and molecular weight were measured for this copolymer. The results are shown in Table 8. Next, GP
When the molecular weight distribution is confirmed with C, Mw / Mn = 1.06,
The shape of a sharp mountain with Mw = 2 × 10 ⁵ was shown.

On the other hand, 3-glycidoxypropyltrimethoxysilane (GPMOS) was added to the above polymerization solution as a silane compound having an epoxy group, and modification was carried out at 60 ° C. for 30 minutes. Isopropyl alcohol was added to this and the solid was dried to obtain a rubbery polymer G-1. When the molecular weight distribution of this polymer was confirmed by GPC, it changed into a bimodal structure of the above-mentioned base portion and a higher molecular weight portion which seems to be coupled with two or more molecules of the polymer. As a result, , The total weight average molecular weight is 38 ×
I was jumping to 10 ⁴ . This polymer, together with other data, is obtained by the polymer A obtained in the above Production Example A.
It is a mixture of polymers having a molecular structure in which the hexamethyleneimino groups having a molecular structure of A-1, A-2 and A-3 are each replaced by a butyl group (a polymer represented by the general formula (II)). confirmed.

This polymer G-1 was kneaded according to the formulation shown in Table 7 and vulcanized at 145 ° C. for 33 minutes, and the physical properties of the obtained vulcanized product were evaluated. The results are shown in Table 8.

Example 2 In Example 2, the amount of 1,3-butadiene monomer and the amount of styrene monomer were changed, and TH
Except that potassium-t-amylate was used instead of F,
The same procedure as in Example 1 was performed. Here, the rubber-like polymer G-2
Got This polymer has a bound styrene content of the copolymer,
It had the same molecular structure as G-1 except that the vinyl content of the butadiene portion was different. The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

Example 3 In Example 3, the amount of 1,3-butadiene monomer and the amount of styrene monomer were changed, and TH
Same as Example 1 except that potassium-t-amylate was used in place of F, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (EHMOS) was used in place of GPMOS as the silane compound having an epoxy group. Went to. Here, a rubbery polymer G-3 was obtained. This polymer is the polymer B-1, B- obtained in the above Production Example B.
It was confirmed that the hexamethyleneimino groups of the molecular structures 2 and B-3 were each a mixture of polymers having a molecular structure of butyl groups (polymers represented by the general formula (II)). The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

Comparative Example 1 Comparative Example 1 was performed in the same manner as in Example 1 except that the silane compound GPMOS having an epoxy group was not used. Here, a rubbery polymer G-4 was obtained. This polymer is a normal butadiene-styrene random copolymer. The results of polymer properties and vulcanized physical properties of the polymer are shown in Table 8.

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1 except that the epoxy group-containing silane compound GPMOS was replaced by methyltriphenoxysilane (MTPOS) having no epoxy group. Here, a rubbery polymer G-5 was obtained. As easily understood from the above Production Example A, this polymer was a polymer in which only methylphenoxysilane groups were bonded to the copolymer and functional groups containing hydroxyl groups were not bonded. The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

Example 4 Dried and nitrogen-substituted 80
In a 0 ml pressure resistant glass container, according to the polymerization prescription in Table 6,
Cyclohexane 315g, 1,3-butadiene monomer 48g, styrene monomer 12g, THF 27.5mm
ol, hexamethyleneimine (HMI) 0.5 mmol
Was added, and n-BuLi was added thereto, and then 2
Polymerization was carried out for a time. From the start to the end of the polymerization, the polymerization system was uniform and transparent with no precipitation observed. The polymerization conversion rate is
Almost 100% (this method is described in Japanese Patent Application No. 5-260).
229).

After that, modification was performed in the same manner as in Example 1 using the copolymer and GPMOS. Here, the polymer G-6
Got This polymer is the polymer A obtained in Production Example A above.
It was confirmed to be a mixture of -1, A-2 and A-3 (a polymer represented by the general formula (I)). The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

Example 5 In Example 5, the amount of 1,3-butadiene monomer and the amount of styrene monomer were changed, and TH
Except that potassium-t-amylate was used instead of F,
The same procedure as in Example 4 was performed. Here, the rubber-like polymer G-7
Got This polymer has a bound styrene content of the copolymer,
It had the same molecular structure as G-6 except that the vinyl content of the butadiene part was different. The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

Example 6 In Example 6, the amount of 1,3-butadiene monomer and the amount of styrene monomer were changed, and TH
Same as Example 4 except that potassium-t-amylate was used in place of F, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (EHMOS) was used in place of GPMOS as the silane compound having an epoxy group. Went to. Here, a rubbery polymer G-8 was obtained. This polymer is the polymer B-1, B- obtained in the above Production Example B.
It was confirmed to be a mixture of 2 and B-3 (a polymer represented by the general formula (II)). The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

Comparative Example 3 Comparative Example 3 was performed in the same manner as in Example 4 except that the silane compound GPMOS having an epoxy group was not used. Here, a rubbery polymer G-9 was obtained. This polymer is a copolymer having a hexamethyleneimino group at the terminal of a usual butadiene-styrene copolymer. The results of polymer properties and vulcanized physical properties of the polymer are shown in Table 8.

Comparative Example 4 Comparative Example 4 was performed in the same manner as in Example 4 except that methyltriphenoxysilane (MTPOS) having no epoxy group was used instead of the silane compound GPMOS having an epoxy group. Here, a rubbery polymer G-10 was obtained. This polymer is the same as that of Production Example A above.
As can be easily understood from the above, it was a polymer in which only the methylphenoxysilane group was bonded to the tertiary amine-terminated copolymer, and the functional group containing a hydroxyl group was not bonded. The results of the properties of the copolymer and the vulcanized physical properties of the polymer are shown in Table 8.

[0109]

[Table 6]

[0110]

[Table 7]

[0111]

[Table 8]

[Molecular Structure of Polymer] Next, the molecular structure of the polymer used in this example was examined. Since it is difficult to confirm amine in a high molecular weight polymer, the amount of n-butyllithium in the polymerization formulation is 50 mmol, HMI is 50 mmol, and potassium-t-amylate is 2.5.
Polymerization was performed in exactly the same manner as in Example 5 except that it was used as mmol to obtain a low molecular weight polymer having a number average molecular weight of 2000. As a result of measuring the nitrogen pigment of this polymer, 0.6
%Met. The theoretical value when one molecule has one amine is 0.7%. From this, the presence of amine in the polymer was confirmed.

In addition, the amount of BuLi was increased as follows, and the amount of the silane compound, imine compound, and randomizer having an epoxy group was increased so that the molar ratio was the same as that of Example 5 with respect to BuLi. Low molecular weight polymers g-1, g-2 and g-3 were prepared in exactly the same manner as in Example 5 (Table 9).

[0114]

Table 9 Base Mn Mw / Mn coupling BuLi addition amount (× 10 ³ ) Efficiency (mmol) g-1 5.11 1.06 73 18 g-2 8.11 1.06 62 12 12 g-3 19. 9 1.05 536

Using the obtained low molecular weight polymer, Si—O and Si—C bonds were observed by IR spectrum. Here, the Si-O bond has a Si-C bond at around 1260 cm ^-1.
It is known that the binding is confirmed as absorption near 1160 cm ^-1 (JP-A-62-227908).
issue). FIG. 1 shows the IR spectrum of the above polymer of the present invention. (A) is an IR spectrum of the unmodified polymer, and (b) is an IR spectrum of the polymer of the present invention.

As shown in FIG. 1, the polymer of this example was
Is 1260 cm^-1And 1190 cm ^-1Respectively, Si
Absorption attributed to —O bond and Si—C bond was observed.
It was Furthermore, as the molecular weight of the polymer decreases, that is, the polymer
As the concentration of Si-O bond and Si-C bond at the end increases,
In addition, the absorption of both bonds is large,
The existence of Si-O and Si-C bonds in
To be

Further, as shown in FIG. 3, in the polymer of this example, absorption attributable to the OH group at the terminal was observed at 3100 to 4000 cm ⁻¹ .

Therefore, from both aspects of the polymer production reaction and the molecular structure analysis, it was confirmed that the polymer of the present invention has a nitrogen-containing functional group, a hydroxyl group and an alkoxysilano group at the polymer terminal.

As can be seen from Table 8, the polymer composition of the present invention has the breaking property, the abrasion resistance and the low hysteresis loss property (t) without increasing the compound Mooney.
It is understood that it is excellent in an δ of 50 ° C.

The above effect of the polymer composition of the present invention becomes more apparent by comparing the examples with the comparative examples. That is, the effect of the functional group (presence or absence) containing a hydroxyl group in the polymer (Examples 1 to 3)
And Comparative Example 2, Examples 4 to 6 and Comparative Example 4), combined use of a functional group containing a hydroxyl group in the polymer and an alkoxysilane group (presence or absence)
(Examples 1 to 3 and Comparative Example 1, Examples 4 to 6 and Comparative Example 3), and effects within the scope of the present invention regardless of the type of functional group containing a hydroxyl group in the polymer (implementation It is obvious from a look at Examples 2 and 3, Examples 5 and 6, and these and other comparative examples.

[0121]

EFFECT OF THE INVENTION The polymer of the present invention and the polymer composition thereof have the above-mentioned constitutions, so that they are excellent in breaking property, abrasion resistance and low hysteresis loss property (low rolling resistance, low fuel consumption). Have.

[Brief description of drawings]

FIG. 1 Si—O bond and Si in the polymer of the present invention
It is an IR spectrum showing the presence of a -C bond.

FIG. 2 Si—O bond and Si in the polymer of the present invention
It is an IR spectrum showing the presence of a -C bond.

FIG. 3 I showing the presence of OH groups in the polymers of the invention
It is an R spectrum.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C08L 15/00 C08K 5/54 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (16)

(57) [Claims] 1. A functional group containing a nitrogen atom is bonded to a terminal portion of a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer, and a functional group having a hydroxyl group is bonded to another portion of the polymer or the copolymer. And a polymer having at least one molecular structure represented by the following general formula (I), in which silicon having at least one alkoxy group is bonded to this functional group. [Chemical 1] (In the formula, P represents a polymer or a copolymer, and R ¹ , R
² , R ⁶ and R ⁷ are aliphatic or alicyclic having 1 to 20 carbon atoms,
Represents a group selected from each aromatic hydrocarbon group, which may be the same or different, and R ³ is a group selected from each aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Represent, R
⁴ represents an oxygen atom, a methylene group or a methylene group having a substituent, and R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. When there are plural OR ⁶ groups, R ⁶ may be the same or different. R ¹ and R ² may combine with each other to form a cyclic structure containing the nitrogen atom, or by forming a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure. Good. x represents an integer of 1 to 3, y represents an integer of 1 to 3, z represents 0 or an integer of 1 to 2, and x + y + z represents an integer of 2 to 4. n represents 0 or 1. ) 2. The polymer is represented by R ¹ and R ^{2 in the} above formula.
As a group selected from aliphatic, alicyclic, and aromatic hydrocarbon groups each having 1 to 13 carbon atoms, or an imine compound residue containing the above nitrogen atom having 2 to 13 carbon atoms formed by bonding to each other. A group selected from the group consisting of 1 to 6 carbon atoms as R ^3.
A group selected from each of the aliphatic and alicyclic hydrocarbon groups of
R ⁴ is an oxygen atom or a methylene group, R ⁵ is a group selected from an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ⁶ is an aliphatic or aromatic hydrocarbon group having 1 to ⁶ carbon atoms. The polymer according to claim 1, which has a group selected from R 1 and a group selected from an aliphatic hydrocarbon group having 1 to 3 carbon atoms and a phenyl group as R ⁷ . 3. The conjugated diene / vinyl aromatic hydrocarbon
If the copolymer is a butadiene / styrene copolymer
In both of the above formulas, R¹And R²With 4 to 12 carbon atoms
Group selected from imine compound residues containing the nitrogen atom
And R³As an aliphatic or alicyclic group having 1 to 6 carbon atoms
Radical and R^FourAnd an oxygen atom or a methylene group as R
^FiveSelected from aliphatic hydrocarbon groups having 1 to 4 carbon atoms
Radical and R ⁶Each of aliphatic and aromatic having 1 to 6 carbon atoms
A group selected from a hydrocarbon group and R ⁷As carbon number 1-3
A group selected from an aliphatic hydrocarbon group and a phenyl group of
The polymer according to claim 1, which comprises: 4. A conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer has a hydrogen atom bonded to a terminal portion thereof, and a functional group having a hydroxyl group bonded to another portion of the polymer or the copolymer, and this functional group. A polymer comprising at least one of the molecular structures represented by the following general formula (II), wherein the polymer has at least one oxy group-bonded silicon group. [Chemical 2] (In the formula, P represents a polymer or a copolymer, R ³ represents a group selected from aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, and R ⁴ represents an oxygen atom, a methylene group or a substituent. Represents a methylene group having R ⁵ , R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ and R ^{7 each} have 1 to 20 carbon atoms.
Represents a group selected from each of aliphatic, alicyclic and aromatic hydrocarbon groups, and may be the same or different. OR ⁶
When there are plural groups, R ⁶ may be the same or different. x is an integer of 1 to 3, y is an integer of 1 to 3, and z is 0.
Alternatively, an integer of 1 to 2 and x + y + z represents an integer of 2 to 4. n represents 0 or 1. ) 5. The polymer, wherein R ³ is a group selected from aliphatic hydrocarbon groups and alicyclic hydrocarbon groups having 1 to 6 carbon atoms as R ³ , and an oxygen atom or a methylene group as R ⁴ . R ⁵
A group selected from an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a group selected from each of aliphatic and aromatic hydrocarbon groups having 1 to ⁶ carbon atoms as R ⁶ , and a group having 1 to 1 carbon atoms as R ⁷ . The polymer according to claim 4, which has a group selected from an aliphatic hydrocarbon group of 3 and a phenyl group. 6. The conjugated diene / vinyl aromatic hydrocarbon
If the copolymer is a butadiene / styrene copolymer
In both of the above formulas, R³As an aliphatic having 1 to 6 carbon atoms and
A group selected from alicyclic groups and R^FourAs an oxygen atom or methyl
Rene group and R ^FiveAs an aliphatic hydrocarbon group having 1 to 4 carbon atoms
A group selected from⁶As an aliphatic having 1 to 6 carbon atoms
And a group selected from aromatic hydrocarbon groups, and R⁷As
Selected from aliphatic hydrocarbon groups having 1 to 3 carbon atoms and phenyl groups.
The group according to claim 4, characterized in that
Coalescing. 7. A conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer has a functional group containing a nitrogen atom bonded to the terminal portion thereof, and a functional group having a hydroxyl group bonded to another portion of the polymer or the copolymer. And a rubber containing 10 parts by weight or more of a polymer having at least one molecular structure represented by the following general formula (I), in which silicon having at least one alkoxy group is bonded to this functional group. A polymer composition comprising 100 parts by weight of a raw material and 10 to 100 parts by weight of a filler containing white carbon. [Chemical 3] (In the formula, P represents a polymer or a copolymer, and R ¹ , R
² , R ⁶ and R ⁷ are aliphatic or alicyclic having 1 to 20 carbon atoms,
Represents a group selected from each aromatic hydrocarbon group, which may be the same or different, and R ³ is a group selected from each aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Represent, R
⁴ represents an oxygen atom, a methylene group or a methylene group having a substituent, and R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. When there are plural OR ⁶ groups, R ⁶ may be the same or different. R ¹ and R ² may combine with each other to form a cyclic structure containing the nitrogen atom, or by forming a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure. Good. x represents an integer of 1 to 3, y represents an integer of 1 to 3, z represents 0 or an integer of 1 to 2, and x + y + z represents an integer of 2 to 4. n represents 0 or 1. ) 8. The conjugated diene / vinyl aromatic hydrocarbon
If the copolymer is a butadiene / styrene copolymer
In both of the above formulas, R¹And R²With 4 to 12 carbon atoms
Group selected from imine compound residues containing the nitrogen atom
And R³As an aliphatic or alicyclic group having 1 to 6 carbon atoms
Radical and R^FourAnd an oxygen atom or a methylene group as R
^FiveSelected from aliphatic hydrocarbon groups having 1 to 4 carbon atoms
Radical and R ⁶Each of aliphatic and aromatic having 1 to 6 carbon atoms
A group selected from a hydrocarbon group and R ⁷As carbon number 1-3
A group selected from an aliphatic hydrocarbon group and a phenyl group of
The polymer composition according to claim 7, which comprises: 9. A conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer has a hydrogen atom bonded to a terminal portion thereof, and a functional group having a hydroxyl group bonded to another portion of the polymer or the copolymer, and this functional group. 100 parts by weight of a rubber material containing 10 parts by weight or more of a polymer having at least one molecular structure represented by the following general formula (II), in which a silicon-containing group having at least one alkoxy group is bonded to the group. And 10 to 100 parts by weight of a filler containing white carbon,
A polymer composition comprising: [Chemical 4] (In the formula, P represents a polymer or a copolymer, R ³ represents a group selected from aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, and R ⁴ represents an oxygen atom, a methylene group or a substituent. Represents a methylene group having R ⁵ , R ⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ and R ^{7 each} have 1 to 20 carbon atoms.
Represents a group selected from each of aliphatic, alicyclic and aromatic hydrocarbon groups, and may be the same or different. OR ⁶
When there are plural groups, R ⁶ may be the same or different. x is an integer of 1 to 3, y is an integer of 1 to 3, and z is 0.
Alternatively, an integer of 1 to 2 and x + y + z represents an integer of 2 to 4. n represents 0 or 1. ) 10. The conjugated diene / vinyl aromatic hydrocarbon copolymer is a butadiene / styrene copolymer, and in the above formula, R ³ is a group selected from aliphatic and alicyclic groups having 1 to 6 carbon atoms; ⁴ is an oxygen atom or a methylene group, R ⁵ is a group selected from aliphatic hydrocarbon groups having 1 to 4 carbon atoms, and R ⁶ is selected from aliphatic and aromatic hydrocarbon groups having 1 to ⁶ carbon atoms. And a group selected from an aliphatic hydrocarbon group having 1 to 3 carbon atoms and a phenyl group as R ⁷ , the polymer according to claim 9. 11. The polymer composition according to claim 7, wherein the filler is 20 to 60 parts by weight with respect to 100 parts by weight of the rubber raw material. 12. The polymer composition according to claim 7, wherein the filler is only white carbon. 13. The polymer composition according to claim 7, wherein the filler is white carbon or carbon black. 14. The rubber raw material 100 is used as the filler.
With respect to parts by weight, the white carbon is 9.9 to 99.
The polymer composition according to claim 7 or 9, containing 9 parts by weight and 0.1 to 90 parts by weight of the carbon black, and 10 to 100 parts by weight. 15. The polymer composition according to claim 7, wherein the white carbon is wet silica. 16. The polymer composition according to claim 7, wherein the polymer composition further comprises a silane coupling agent.