JP3514824B2 - 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 breaking properties, abrasion resistance and low hysteresis loss properties (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 higher compatibility of 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 alkoxy groups is not sufficient and the obtained polymer is a one-end modified polymer. 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-62-22).
7908), both ends are modified with alkoxysilane,
Since this has a coupling ability, it is practically difficult to control the molecular weight, the viscosity of the polymer cement before and after modification becomes high, and problems occur in steam strip resistance and change over time of the produced bulk polymer.

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 uses a novel polymer excellent in breaking properties, abrasion resistance and low hysteresis loss properties (low rolling resistance, low fuel consumption) without impairing wet grip properties, and a novel polymer. The purpose of the present invention is to provide a polymer composition.

[0012]

According to a first aspect of the present invention, a polymer of the present invention has a functional group containing a nitrogen atom bonded to a terminal portion of a conjugated diene polymer or a conjugated diene / vinyl aromatic hydrocarbon copolymer, and It is characterized by comprising at least one of the molecular structures represented by the following general formula (I), in which silicon having at least one alkoxy group is bonded to another part of the polymer or the copolymer.

[0013]

[Chemical 3]

(In the formula, P represents a polymer or a copolymer, and R ¹ and R ² are bonded to each other and have 4 to 4 carbon atoms.
Selected from 12 imine compound residues containing the nitrogen atom
Represents a group, and R ³ and R ⁴ represent a group selected from aliphatic, alicyclic, and aromatic hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different. When there are plural OR ³ groups, R ³ may be the same or different. Also,
R ¹ and R ² may combine with each other to form a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure formed. n is an integer of 1 to 3, m is an integer of 1 to 3, and n + m is an integer of 2 to 4. )

According to a second aspect of the present invention, in the first aspect, the conjugated diene polymer is a polybutadiene polymer.

The polymer according to claim 3 is the polymer according to claim 1, wherein the conjugated diene / vinyl aromatic hydrocarbon copolymer is a butadiene / styrene copolymer.

The polymer according to claim 4 is the polymer according to claims 1 to 3.
In the above formula, in the above formula, R ³ is a group selected from aliphatic, alicyclic, and aromatic hydrocarbon groups having 1 to 10 carbon atoms, and R ⁴ is a fatty group having 1 to 10 carbon atoms. And a group selected from a group hydrocarbon group.

[0018]

The polymer of claim 5, wherein, in claim 4, wherein the polymer is in the formula, 1 to 6 carbon atoms as R ³
And a group selected from the group consisting of aliphatic groups and aromatic groups.

[0020]

[0021]

The polymer composition of the present invention is, as a sixth aspect , 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 or the copolymer. A rubber raw material 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 another part of 100 parts by weight and 10 to 100 parts by weight of a filler containing white carbon are included.

[0023]

[Chemical 4]

(In the formula, P represents a polymer or a copolymer, and R ¹ and R ² are bonded to each other and have 4 to 4 carbon atoms.
Selected from 12 imine compound residues containing the nitrogen atom
Represents a group, and R ³ and R ⁴ represent a group selected from aliphatic, alicyclic, and aromatic hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different. When there are plural OR ³ groups, R ³ may be the same or different. Also,
R ¹ and R ² may combine with each other to form a heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) in the cyclic structure formed. n is an integer of 1 to 3, m is an integer of 1 to 3, and n + m is an integer of 2 to 4. )

The polymer composition according to claim 7 is the polymer composition according to claim 6.
In the above, the conjugated diene polymer is a polybutadiene polymer.

The polymer composition according to claim 8 is the polymer composition according to claim 9.
In the above, the conjugated diene / vinyl aromatic hydrocarbon copolymer is a butadiene / styrene copolymer.

The polymer composition according to claim 9 is the polymer composition according to claim 6.
To the 8, wherein the polymer is the above formula, an aliphatic having 1 to 10 carbon atoms as R ^3, alicyclic, and a group selected from the hydrocarbon group of the aromatic, C1-10 as R ⁴ And a group selected from the aliphatic hydrocarbon groups of.

[0028]

The polymer composition according to claim 10 is
9 , wherein the polymer has a group represented by R ^{3 in the} above formula, which is selected from aliphatic and aromatic groups having 1 to 6 carbon atoms.

[0030]

[0031]

[0032] Claim 11 polymer composition according the claim
6 , the amount of the filler is 20 to 60 parts by weight with respect to 100 parts by weight of the rubber raw material.

The polymer composition according to claim 12 is the compound according to claim
In item 6 , the filler is only white carbon.

A polymer composition according to claim 13 is
In item 6 , the filler is white carbon or carbon black.

The polymer composition according to claim 14 is
13 , the filler contains both 9.9 to 99.9 parts by weight of the white carbon and 0.1 to 90 parts by weight of the carbon black with respect to 100 parts by weight of the rubber raw material, It is characterized by being 100 parts by weight.

A polymer composition according to claim 15 is
6 or 13 is characterized in that the white carbon is wet silica.

The polymer composition of claim 16 is
6 , the polymer composition further comprises a silane coupling agent.

The present inventor has found that the constituents of the polymer, the filler,
As a result of intensive investigations focusing on those physical properties, for example, a polymer having a molecular structure of tertiary amine / butadiene-styrene random copolymer / alkoxysilane and a polymer composition containing this polymer and white carbon The inventors have found that the object of the present invention is achieved, and have completed the present invention.

This effect is exhibited by the fact that the surface of white carbon such as silica contained in the filler can react with the alkoxysilano functional group in the polymer, and further the tertiary amine is bound to the polymer terminal. It is considered that

The present invention will be described in detail below. P represented by the general formula (I) 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. This conjugated diene monomer has 4 to 12 carbon atoms per molecule.
And preferably 4 to 8 conjugated diene hydrocarbons. For example, 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, octadiene and the like can be mentioned. These may be used alone or in combination of two or more, and 1,3-butadiene is particularly preferable.

The conjugated diene / vinyl aromatic hydrocarbon copolymer is a copolymer composed of a conjugated diene unit and a vinyl aromatic hydrocarbon unit, each of which is obtained by copolymerization of a conjugated diene monomer and a vinyl aromatic hydrocarbon unit.
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 copolymer is not particularly limited, but usually takes a microstructure within the range obtained by the organolithium catalyst system. be able to. The composition of the conjugated diene / vinyl aromatic hydrocarbon copolymer such as butadiene / styrene copolymer is not particularly limited, but is usually 30/70.
A weight ratio of ˜95 / 5 is used, and the composition distribution of the copolymer can take a random structure, a block structure or an intermediate structure thereof, but a random structure or an intermediate structure is usually preferable.

As shown in the general formula (I), a functional group containing a nitrogen atom is bonded to the terminal portion of the polymer or copolymer.

The functional group containing a nitrogen atom is represented by R ¹ R ² N-, R ¹ and R ² are bonded to each other, it will form a ring structure containing a nitrogen atom, or even hetero this ring structure It represents that a heterocyclic structure containing an atom (oxygen atom or nitrogen atom) may be formed, that is, it forms a residue of an imine compound.

[0045]

Examples of the imine compound include pyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine, heptamethyleneimine, Dodecamethyleneimine, coniine, morpholine, N-methylpiperazine, N
-Ethylpiperazine, N-methylimidazolidine, N-
Examples thereof include ethylimidazolidine, oxazine, pyrroline, pyrrole and azepine.

R ³ and R ⁴ represented by the general formula (I)
Each represents a group selected from an aliphatic, alicyclic, and aromatic hydrocarbon group having 1 to 20 carbon atoms, preferably an aliphatic, alicyclic, and aromatic group having 1 to 10 carbon atoms. It represents a group selected from hydrocarbon groups. Examples of the aliphatic hydrocarbon group include groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups, with a methyl group, an ethyl group and an n-propyl group being preferred. Examples of the alicyclic hydrocarbon group include groups such as cyclopentyl, cyclohexyl, and cycloheptyl, with a cyclohexyl group being preferred. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthryl, and phenanthryl groups, with the phenyl group being preferred. Most preferably, R ³ represents a group selected from aliphatic and aromatic groups having 1 to 6 carbon atoms from the viewpoint of further improving the fracture characteristics and low hysteresis loss. R ⁴ does not exist in the polymer depending on the number of polymers containing OR ³ and nitrogen bonded to silicon in the polymer (when n + m = 4 in the general formula (I)).

In the general formula (I), n is an integer of 1 to 3 and m is an integer of 1 to 3, provided that the sum of n and m, that is, n + m is an integer of 2 to 4. . When n is 1, m is 1
When 3 and n are 2, m is 1 to 2 and when n is 3, m is 1. Therefore, the number of R ⁴ is determined in each case. The production method of the polymer of the present invention will be described later, but depending on production conditions, n and m can be changed within the range satisfying the above conditions,
There is no particular limitation. In some cases, n and m are fixed to be a single polymer, and in some cases, n and m are a mixture of a plurality of different polymers. Usually, it is often the latter mixture.

The polymer represented by the general formula (I) is a combination of the above-mentioned molecular structural elements, and in order to further improve various physical properties, and when it is made into a polymer composition, it is combined with silica described later. to improve interaction significantly, aliphatic having 1 to 10 carbon atoms as R ^3, alicyclic, and a group selected from the hydrocarbon group of the aromatic, aliphatic having 1 to 10 carbon atoms as R ⁴ And a group having a group selected from aromatic hydrocarbon groups are preferable.

Preferred examples of the above polymer include a polymer having a hexamethyleneimine residue as a nitrogen-containing functional group, an ethyl group as R ³ and a phenyl group as R ⁴ , and a hexamethyleneimine residue as a nitrogen-containing functional group. A polymer having an n-propyl group as R ³ and an optional methyl group as R ⁴ , a polymer having a hexamethyleneimine residue as a nitrogen-containing functional group, an n-propyl group as R ³ , and a phenyl group as R ^4. A polymer having a hexamethyleneimine residue as a nitrogen-containing functional group, a phenyl group as R ³ and a methyl group as an optional R ⁴ , a hexamethyleneimine residue as a nitrogen-containing functional group and a phenyl group as R ^3. R ⁴
A polymer having a phenyl group as a group, a polymer having a dodecamethyleneimine residue as a nitrogen-containing functional group, an ethyl group as R ³ and a methyl group as an optional R ⁴ , a dodecamethyleneimine residue as a nitrogen-containing functional group And a polymer having an ethyl group as R ³ and a phenyl group as R ⁴ , a polymer having a dodecamethyleneimine residue as a nitrogen-containing functional group, a phenyl group as R ³ , and an optional methyl group as R ^4. A polymer having a dodecamethyleneimine residue as a functional group, a phenyl group as R ³ , and a phenyl group as R ⁴ , a piperidine residue as a nitrogen-containing functional group, an ethyl group as R ³ , and a methyl group as optional R ^4. A polymer having, a piperidine residue and R as a nitrogen-containing functional group
A polymer having an ethyl group as ³ and a phenyl group as R ⁴ , a polymer having a piperidine residue as a nitrogen-containing functional group, a phenyl group as R ³ , and a methyl group as an optional R ⁴ , a nitrogen-containing functional group Examples thereof include a polymer having a piperidine residue, a phenyl group as R ³ , and a phenyl group as R ⁴ . Here, the optional R ⁴ means R ⁴ with or without R ⁴ , and with or without R ⁴ . When R ⁴ is not present, n + m = 4 in the formula as described above.
Corresponds to the case of.

The molecular structure of the polymer is shown in the following examples of the method for producing the polymer.

The polymer of the present invention has a lithium active terminal after a monomer is added to a lithium amide initiator obtained from an imine compound such as hexamethyleneimine and an organolithium compound to initiate polymerization of the monomer. It can be obtained by adding an alkoxysilane compound to the polymer solution.

In addition to the above method, the polymer of the present invention is obtained by polymerizing a monomer using a lithium amide catalyst as an initiator by adding an imine compound in the presence of at least a monomer and further adding an organic lithium compound. And then adding an alkoxysilane compound to the polymer solution having a lithium active end.

The method for producing the polymer of the present invention is not particularly limited, but from the viewpoint of handling stability, initiation efficiency, reproducibility, coupling property, etc. of the initiator component used in producing the polymer, the latter The above method can be more preferably used.

Here, in the case where the polymer of Reference Example was produced by the latter method, butadiene (B) and styrene (S) were used as monomers (the copolymer is BSP), and diethylamine (DE) was used as the secondary amine compound.
A) is shown below as Production Example A using methyltriethoxysilane (MTEOS) as the alkoxysilane compound. The obtained polymer is A-1 and / or A-
It becomes 2. A book similar to A except that the imine compound hexamethyleneimine (HMI) was used in place of DEA, and tetraphenoxysilane (TPOS) was used in place of MTEOS.
A production example of the invention is shown in B. The obtained polymer is B-1, B
-2 and / or B-3.

[0056]

[Chemical 5]

[0057]

[Chemical 6]

The alcohol used in the method for producing the polymer of the present invention
The coroxysilane compound has the general formula (I) of the polymer of the present invention.
-Si (R in the molecular structure represented by^Four _{4- (m + n)})-(OR
³ ) _mA compound for forming moieties, alkoxy
As the silane compound, a tetraalkoxysilane compound,
Alkylalkoxysilane compounds, arylalkoxy
Silane compounds, alkenylalkoxysilane compounds, Ha
Logenoalkoxysilane compounds can be used.
There is no particular limitation. In addition, with the alkoxy group in the text
Is a hydrocarbon group in which a hydrogen atom of a hydroxyl group is replaced
Is an alkoxy group when it is aliphatic, or an aromatic group
Aryloxy group, aralkyl when it is an aralkyl group
It refers to all groups such as a rualkyloxy group.

Examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra- (2-ethyl-hexanoxy) silane, tetraphenoxysilane and tetratoluy. Roxysilane etc. are mentioned.

Examples of the alkylalkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-n-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and ethyltriethoxysilane. -N-propoxysilane, ethyltri-n-butoxysilane, ethyltriphenoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-
Examples thereof include n-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane and the like.

Examples of the arylalkoxysilane compound include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-n-butoxysilane and phenyltriphenoxysilane.

Examples of the alkenylalkoxysilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane,
Examples thereof include vinyltri-n-butoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, octenyltrimethoxysilane, divinyldimethoxysilane, and styryltrimethoxysilane.

Examples of the halogenoalkoxysilane compound include trimethoxychlorosilane, triethoxychlorosilane, tri-n-propoxychlorosilane, tri-n-butoxychlorosilane, triphenoxychlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane and di-n. -Propoxydichlorosilane, diphenoxydichlorosilane, methoxytrichlorosilane, ethoxytrichlorosilane, n-propoxytrichlorosilane, phenoxytrichlorosilane, trimethoxybromosilane, triethoxybromosilane, tri-n-propoxybromosilane, triphenoxybromosilane , Dimethoxydibromosilane, diethoxydibromosilane,
Di-n-propoxydibromosilane, diphenoxydibromosilane, methoxytribromosilane, ethoxytribromosilane, n-propoxytribromosilane, phenoxytribromosilane, trimethoxyiodosilane,
Triethoxyiodosilane, tri-n-propoxyiodosilane, triphenoxyiodosilane, dimethoxydiiodosilane, di-n-propoxydiiodosilane, diphenoxydiiodosilane, methoxytriiodosilane, ethoxytriiodosilane, n- Examples include propoxytriiodosilane and phenoxytriiodosilane.

In this production method, those used as the polymerization solvent include, for example, 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 used as the polymerization initiator in this production method includes n-butyllithium, ethyllithium, propyllithium, tert-butyllithium, hexyllithium, 1,4-dilithiobutane, butyllithium and divinylbenzene. Examples thereof include alkyllithium as a reaction product, alkylenedilithium, phenyllithium, stilbendilithium, or the like, or organometallic lithium such as tributyltinlithium, lithium amide such as lithium hexamethyleneimide, lithium diethylamide, or lithium pyrrolidide. These lithium initiators may be used alone or in combination of two or more. For example, when alkyl lithium is used in combination with a secondary amine compound or an imine compound in a polymerization system as an initiator, n-butyl lithium, sec-butyl lithium, or the like as the alkyl lithium is soluble in a hydrocarbon solvent and has an initiation rate. On the other hand, when a lithium amide-based initiator is used from the beginning, lithium hexamethylene imide, lithium pyrrolidide, lithium dihexyl amide and the like are soluble in a hydrocarbon solvent and white carbon, for example, It is preferable from the viewpoint of reinforcing property against silica and the like. 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) The complex of an alkali metal with a ketone or a phosphite triester includes 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 the above-mentioned (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 essentially maintain the liquid phase.
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 performed by adding the alkoxysilane compound after the polymerization is carried out in an atmosphere that does not deactivate the active terminal lithium of the polymer or copolymer.

After the reaction is completed, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to coagulate the polymer, and then the polymer is dried 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 add 10 parts by weight or more of the polymer to 100 parts by weight of the rubber raw material, and preferably 40 parts by weight or more in order to sufficiently 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.

Examples of the white carbon used include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate, clay, talc, calcium carbonate, basic magnesium carbonate, and alumina hydrate. Thing, diatomaceous earth, barium sulfate, mica,
Wet silica containing alumina sulfate, titanium oxide and the like, among which the effect of improving fracture characteristics and the effect of simultaneously achieving both wit grip properties and low rolling resistance are most remarkable, is preferable.

The amount of the filler to be blended is 10 to 100 parts by weight based on 100 parts by weight of the rubber raw material. From the viewpoint of the reinforcing property by the white carbon contained in the filler and the efficiency of improving various physical properties due to 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 reinforcing property and efficiency of improving various physical properties. If the amount is less than 10 parts by weight, the fracture characteristics and the like are not sufficient, and if it exceeds 100 parts by weight, the workability is poor.

Further, the filler used in the polymer composition of the present invention may be white carbon or carbon black, whereby the effect of improving various physical properties becomes great. As usable carbon black, 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 within the range of the filler with respect to 100 parts by weight of the raw rubber from the viewpoint of reinforcing properties and processability. In 0.1 to 90 parts by weight of carbon black and 9.9
It is preferable to blend ˜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 are preferable from the viewpoint of improving the reinforcing property effect. Further, as other examples, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N , N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazole tetrasulfide.

The addition amount of the silane coupling agent to be added to the polymer composition can be made lower than the usual addition amount while maintaining the same physical properties. From the viewpoint of rubber raw material 1
It is 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 00 parts by weight.

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 it is less than 0.1 part by weight, the breaking strength, abrasion resistance and low hysteresis loss of the vulcanized rubber will be deteriorated, and if it exceeds 5 parts by weight, rubber elasticity will be lost.

Examples of the process oil that can be used in the polymer composition of the present invention include paraffin type oil, naphthene type oil, aromatic type oil 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 that 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.

[0095]

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.

As an index of hysteresis loss property, tan δ
(50 ° C.) was used. The smaller tan δ (50 ° C),
It is evaluated to have low hysteresis loss. tan δ (5
The measurement was performed at a temperature of 50 ° C., a strain of 8%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Rheometrics). Wet grip index tan δ (0
(° C) was measured using the same device at a temperature of 0 ° C, a strain of 1% and a 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.

Reference Example 1 In a dry, nitrogen-substituted 800 ml pressure-resistant glass container, according to the formulation in Table 1, 315 g of cyclohexane,
36 g of 1,3-butadiene monomer, 24 g of styrene monomer, potassium-t-amylate 0.025 mmo
1, di-n-hexylamine (DHA) 0.5 mmol
Of n-butyllithium (BuLi) 0.
After adding 5 mmol, it superposed | polymerized at 50 degreeC for 2 hours.
From the start to the end of the polymerization, the polymerization system was uniform and transparent with no precipitation observed. The polymerization conversion rate was almost 100% (this method is described in Japanese Patent Application No. 5-260229). 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 of this copolymer were measured. Including the reference example 1, the following example 2
4 and Comparative Examples 1 to 6 had a bound styrene content of 39 to 41% and a vinyl content of butadiene portion of 14 to 16%. The weight average molecular weight before terminal modification was 20 × 10 ^{4 to} 22 × 10 ⁴ , and the molecular weight distribution was 1.05 to 1.12.

On the other hand, methyltriethoxysilane (MTEO) was added to the above polymerization solution as an alkoxysilane compound.
S) was added and denaturation was performed at 60 ° C. for 30 minutes. Isopropyl alcohol was added to this and the solid was dried to obtain a rubbery polymer G-1. It was confirmed that this polymer was a mixture of the polymers A-1 and A-2 obtained in Production Example A above. Including Reference Example 1, as in Examples 2 to 4 and Comparative Examples 2 to 4 below, the weight average molecular weight of the polymer after modification by adding an alkoxysilane compound to the copolymer is 31 × 10 ⁴ to 43 × 10. ^{Was 4} . On the other hand, the polymers of Comparative Examples 1, 5, and 6 had a weight average molecular weight of 20 × 10 ^4.
It was ˜22 × 10 ⁴ .

This polymer G-1 was kneaded according to the formulation shown in Table 2 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 3.

Example 2 Example 2 was carried out in the same manner as in Reference Example 1, except that the imine compound hexamethyleneimine (HMI) was used in place of DHA. Here, a rubbery polymer G-2 was obtained. This polymer is the polymer A-1 and A-2 obtained in Production Example A above.
It was confirmed that the secondary amino group of the above-mentioned molecular structure is a mixture of the polymers of the molecular structure in which each is a hexamethyleneimino group.

The results of vulcanized physical properties of the polymer are shown in Table 3. Example 3 Example 3 was performed in the same manner as in Reference Example 1 except that HMI was used instead of DHA, and tetraphenoxysilane (TPOS) 0.188 mmol was used instead of MTEOS as the alkoxysilane compound. Here, the rubber-like polymer G
-3 was obtained. It was confirmed that this polymer was a mixture of the polymers B-1, B-2 and B-3 obtained in Production Example B above.

The results of vulcanized physical properties of the polymer are shown in Table 3. [Example 4] Example 4 was performed in the same manner as in Reference Example 1 except that HMI was used instead of DHA, and methyltriphenoxysilane (MTPOS) was used instead of MTEOS as the alkoxysilane compound. Here, a rubber polymer G-4 was obtained. This polymer is a mixture of polymers having a molecular structure in which the phenoxysilane groups having the molecular structures of the polymers B-1, B-2 and B-3 obtained in Production Example B are each a methylphenoxysilane group. Was confirmed.

The results of vulcanized physical properties of the polymer are shown in Table 3. Comparative Example 1 Comparative Example 1 was performed in the same manner as Reference Example 1 except that the secondary amine compound DHA and the alkoxysilane compound MTEOS were not used. Here, a rubbery polymer G-5 was obtained. This polymer is a normal butadiene-styrene random copolymer.

The vulcanized physical properties of the polymer are shown in Table 3. Comparative Example 2 In Comparative Example 2, the secondary amine compound DHA was not used, and TP was used as the alkoxysilane compound instead of MTEOS.
The same procedure as in Reference Example 1 was performed except that 0.188 mmol of OS was used. Here, a rubbery polymer G-6 was obtained. This polymer was a polymer in which only a phenoxysilane group was bonded to the copolymer and a functional group containing nitrogen was not bonded, as can be easily seen from the above Production Example B.

The vulcanized physical properties of the polymer are shown in Table 3. Except Comparative Example 3 Comparative Example 3 using no secondary amine compound DHA, ginseng
It was carried out in the same manner as considered in Example 1. Here, a rubbery polymer G-7 was obtained. As easily understood from the above Production Example A, this polymer was a polymer in which only methylethoxysilane groups were bonded to the copolymer and functional groups containing nitrogen were not bonded.

The vulcanized physical properties of the polymer are shown in Table 3. [Comparative Example 4] In Comparative Example 4, the secondary amine compound DHA was not used, and MTP was used as the alkoxysilane compound instead of MTEOS.
Except for using the OS, was carried out in the same manner as in Reference Example 1. here,
A rubbery polymer G-8 was obtained. As easily understood from the above Production Example B, this polymer was a polymer in which only a methylphenoxy group was bonded to the copolymer and a functional group containing nitrogen was not bonded.

The physical properties of the vulcanized polymer are shown in Table 3. Comparative Example 5 Comparative Example 5 was performed in the same manner as Reference Example 1 except that the alkoxysilane compound MTEOS was not used. Here, a rubbery polymer G-9 was obtained. As easily understood from Production Example A above, this polymer was a polymer in which only dihexylamino groups were bonded to the copolymer and alkoxysilane groups were not bonded.

The vulcanized physical properties of the polymer are shown in Table 3. Comparative Example 6 Comparative Example 6 was carried out in the same manner as in Reference Example 1 except that HMI, which is an imine compound, was used instead of DHA and that the alkoxysilane compound, MTEOS was not used. Here, the rubber-like polymer G
-10 was obtained. As easily understood from the above Production Example B, this polymer was a polymer in which only the hexamethyleneimino group was bonded and the alkoxysilane group was not bonded to the copolymer.

The vulcanized physical properties of the polymer are shown in Table 3.

[0114]

[Table 1]

[0115]

[Table 2]

[0116]

[Table 3]

[Molecular Structure of Polymer] Next, the molecular structure of the polymer used in this example was examined.

Since it is difficult to confirm the amine in the high molecular weight polymer, the amount of n-butyllithium in the polymerization prescription is 50 mm.
Example 3 except that ol, HMI was 50 mmol, and potassium-t-amylate was 2.5 mmol.
Polymerization was carried out in the same manner as above to obtain a low molecular weight polymer having a number average molecular weight of 2000. The nitrogen content of this polymer was measured and found to be 0.6%. The theoretical value when one molecule has one amine is 0.7%. From this, the presence of amine in the polymer was confirmed.

Further, except that the amount of BuLi was increased as follows and the amount of the alkoxysilane compound, the imine compound, and the randomizer was increased so that the molar ratio was the same as that of Example 2 with respect to BuLi, it was completely the same as Example 2. Similarly, low molecular weight polymers g-1, g-2 and g-3 were produced (Table 4).

[0120]

Table 4 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, IR spectrum was measured by a thin film method using FT-IR1650 type manufactured by Perkin Elmer Co., Ltd., and Si--O and Si--C were measured.
Binding was observed. Here, the Si-O bond is 1260 cm.
Around ^-1, Si-C bonds are known to be confirmed as the absorption near 1160 cm ^-1 (JP 62
-227908). FIG. 1 shows an IR spectrum of the above polymer of the present invention. (A) is an IR spectrum of the unmodified polymer, (b)
FIG. 3 is an IR spectrum of the above polymer of the present invention. Further, FIG. 2 is a superposition of IR spectra of the unmodified polymer and the polymer of g-1.

As shown in FIGS. 1 and 2, the polymer of this example contained 1260 cm ^-1 and 1190 cm ^-1 respectively.
Absorption attributed to Si-O bond and Si-C bond was observed. Further, as the molecular weight of the polymer decreases, that is, as the concentration of the Si—O bond and the Si—C bond at the end of the polymer increases, the absorption of both of these bonds increases. The existence of O-bonds and Si-C bonds is confirmed.

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 and an alkoxysilano group at the polymer terminal.

Further, as is clear from Table 3, the polymer composition of the present invention is excellent in fracture characteristics, abrasion resistance and low hysteresis loss (tan δ50 ° C.) without impairing wet grip properties (tan δ0 ° C.). You can see that

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 containing nitrogen in the polymer (presence or absence) (Examples 2 to 4 and Comparative Examples 2 to 4), the effect of the alkoxysilane group in the polymer (presence or absence) (Compared with Examples 2 to 4) Examples 5 to 6), effects of combined use (presence or absence) of a functional group containing nitrogen and an alkoxysilane group in the polymer (Examples 2 to 4 and Comparative Example 1), within the scope of the present invention, in the polymer. Regardless of the type of alkoxysilane group of (Examples 2, 3 and 4, these and other comparative examples)
It is obvious at first glance.

[0126]

EFFECT OF THE INVENTION The polymer of the present invention and the polymer composition thereof have the above-mentioned constitutions. Therefore, the breaking property, abrasion resistance and low hysteresis loss property (low rolling resistance, low It has an excellent effect on fuel economy.

[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.

Claims (16)

(57) [Claims] 1. A conjugated diene polymer or conjugated diene / vinyl aromatic hydrocarbon copolymer having a nitrogen atom-containing functional group attached to the terminal portion thereof and having at least one alkoxy group in another portion of the polymer or copolymer. A polymer comprising at least one of the molecular structures represented by the following general formula (I), in which silicon is bonded. [Chemical 1] ( Wherein P represents a polymer or a copolymer, R ¹ and
R ² is a nitrogen atom having 4 to 12 carbon atoms which is formed by bonding with each other.
Represents a group selected from imine compound residues containing elementary atoms,
R ³ and R ⁴ represent groups selected from aliphatic, alicyclic, and aromatic hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different. When there are plural OR ³ groups, R ³ may be the same or different. R ¹ and R ² are
A heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) may be further formed in the cyclic structure formed by bonding with each other . n is an integer of 1 to 3, m is an integer of 1 to 3, and n +
m represents an integer of 2 to 4. ) 2. The polymer according to claim 1, wherein the conjugated diene polymer is a polybutadiene polymer. 3. The polymer according to claim 1, wherein the conjugated diene / vinyl aromatic hydrocarbon copolymer is a butadiene / styrene copolymer. 4. In the above formula, the polymer is a group selected from aliphatic, alicyclic, and aromatic hydrocarbon groups having 1 to 10 carbon atoms as R ³ , and 1 to 1 carbon atoms as R ⁴ . The polymer according to any one of claims 1 to 3, having a group selected from the group consisting of 10 aliphatic hydrocarbon groups. 5. The polymer according to claim 4, wherein in the formula , R ³ has a group selected from aliphatic and aromatic groups having 1 to 6 carbon atoms as R ³ . 6. A conjugated diene polymer or conjugated diene / vinyl aromatic hydrocarbon copolymer having a nitrogen atom-containing functional group attached to a terminal portion thereof and having at least one alkoxy 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 (I) containing a silicon bond is used.
A polymer composition comprising 100 parts by weight of a rubber raw material in an amount of 10 parts by weight or more, and 10 to 100 parts by weight of a filler containing white carbon. [Chemical 2] ( Wherein P represents a polymer or a copolymer, R ¹ and
R ² is a nitrogen atom having 4 to 12 carbon atoms which is formed by bonding with each other.
Represents a group selected from imine compound residues containing elementary atoms,
R ³ and R ⁴ represent groups selected from aliphatic, alicyclic, and aromatic hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different. When there are plural OR ³ groups, R ³ may be the same or different. R ¹ and R ² are
A heterocyclic structure containing a hetero atom (oxygen atom or nitrogen atom) may be further formed in the cyclic structure formed by bonding with each other . n is an integer of 1 to 3, m is an integer of 1 to 3, and n +
m represents an integer of 2 to 4. ) 7. The polymer composition according to claim 6, wherein the conjugated diene polymer is a polybutadiene polymer. 8. The polymer composition of claim 6, wherein the conjugated diene / vinyl aromatic hydrocarbon copolymer is a butadiene / styrene copolymer. 9. In the above formula, the polymer is a group selected from aliphatic, alicyclic and aromatic hydrocarbon groups having 1 to 10 carbon atoms as R ³ , and 1 to 1 carbon atoms as R ⁴ . The polymer composition according to any one of claims 6 to 8 , having a group selected from the group consisting of 10 aliphatic hydrocarbon groups. Wherein said polymer is in the above formula, the polymer composition according to claim 9, characterized in that it comprises a group selected from aliphatic and aromatic having from 1 to 6 carbon atoms as R ^3. 11. The polymer composition according to claim 6 , 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 6 , wherein the filler is only white carbon. 13. The polymer composition according to claim 6 , wherein the filler is white carbon or carbon black. 14. The white carbon is 9.9 to 99.9 with respect to 100 parts by weight of each rubber raw material.
The polymer composition according to claim 13 , wherein the polymer composition contains 10 parts by weight of the carbon black and 0.1 to 90 parts by weight of the carbon black. 15. The polymer composition according to claim 6 or 13 , wherein the white carbon is wet silica. 16. The polymer composition according to claim 6, wherein the polymer composition further comprises a silane coupling agent.