JP2001139633A - Production method for conjugated diene polymer, and rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conjugated diene polymer which has a narrow mol.wt. distribution, is excellent in abrasion resistance and mechanical properties, and has been improved in cold flow. SOLUTION: A conjugated diene compound is polymerized in the presence of a rare earth element compound catalyst mainly comprising (a) a rare earth element-containing compound or its reaction product with a Lewis base, (b) an almoxane and/or an organoaluminum compound, and (c) a halogen-containing compound. The resultant polymer is reacted with a modifier which comprises an alkoxysilane compound having at least one epoxy and/or isocyanate group in the molecule, as an essential ingredient, combined with at least one compound selected from the group consisitng of halogenated organometallic compounds, halogenated metallic compounds, organometallic compounds, heterocumulene compounds, hetero-tricyclic compounds, halogenated isocyano compounds, carboxylic acids, acid halides, ester compounds, carbonate compounds, acid anhydrides, and metal carboxylates.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a conjugated diene-based polymer, and more particularly, to a method for polymerizing a conjugated diene-based compound using a novel rare earth element compound catalyst and then immediately after the polymerization. The present invention relates to a method for producing a conjugated diene polymer having excellent abrasion resistance and mechanical properties, particularly improved cold flow, by reacting a polymer with a specific modifier in combination of two or more kinds.

[0002]

2. Description of the Related Art Numerous proposals have been made for polymerization catalysts for conjugated dienes, and they play an extremely important role industrially. Particularly, in order to obtain a conjugated diene-based polymer having improved thermal and mechanical properties, many polymerization catalysts giving a high cis-1,4 bond content have been studied and developed. For example, composite catalyst systems based on transition metal compounds such as nickel, cobalt, and titanium are known. Some of them are already widely used industrially as polymerization catalysts for butadiene, isoprene and the like [End. Ing. Chem. , 4
8, 784 (1956), and JP-B-37-8198].

On the other hand, in order to achieve a higher cis-1,4 bond content and excellent polymerization activity, a composite catalyst system comprising a rare earth metal compound and a group I-III organometallic compound has been researched and developed, and has a high stereospecificity. Research on the nature polymerization has been actively conducted. In Japanese Patent Publication No. 47-14729,
A catalyst system comprising a rare earth metal compound such as cerium octanoate and an alkyl aluminum hydride such as diisobutyl aluminum hydride or an aluminum hydride such as trialkyl aluminum and ethyl aluminum dichloride is disclosed. In particular, the publication discloses that aging the catalyst in the presence of butadiene increases the catalytic activity.

Further, Japanese Patent Publication Nos. 62-1404, 63-64444 and 1-16244 disclose a catalyst activity by increasing the solubility of a compound in a rare earth element polymerization solvent. Ways to enhance it have been proposed. Furthermore, Japanese Patent Publication No. Hei 4-2601 discloses that a catalyst system comprising a rare earth metal compound, a trialkylaluminum or aluminum hydride, and an organic halogen derivative exhibits higher activity than before in the polymerization of 1,3-butadiene. ing. However, a polymer obtained by a conventional catalyst system containing a rare earth metal compound has a wide molecular weight distribution, and the abrasion resistance and the rebound resilience are not sufficiently improved.

Further, Japanese Patent Application Laid-Open No. 6-212916,
JP-A-6-306113, JP-A-8-73515
In Japanese Patent Application Laid-Open Publication No. H11-146, it is reported that a conjugated diene polymer having high polymerization activity and a narrow molecular weight distribution can be obtained by using a catalyst system using methylalumoxane as a neodymium compound. However, in order to maintain a sufficient catalytic activity and obtain a polymer having a narrow molecular weight distribution by the above polymerization method, it is necessary to use a large amount of alumoxane as compared with a catalyst system using a conventional organoaluminum compound. . For this reason, it is necessary to remove a large amount of metal remaining in the polymer. In addition, the price is higher than ordinary organoaluminum compounds, the cold flow is large, and there are problems in storage stability and the like.

To solve these problems, Japanese Patent Laid-Open No. Hei 10-30
No. 6113, JP-A-11-35633,
It has been reported that a conjugated diene polymer polymerized with a catalyst system using methylalumoxane is modified with a hetero three-membered ring compound, a metal halide compound, a metal carboxylate, or the like to suppress cold flow. However, in order to suppress the cold flow by the above method, the catalyst level is high, and the amount of alumoxane used has not been reduced to a practical level.

[0007]

The inventors of the present invention have conducted intensive studies and as a result, have found that when a catalyst system combining a rare earth metal compound, alumoxane and / or organoaluminum and a halogen-containing compound is used, the amount of alumoxane used can be reduced. A conjugated diene-based polymer having a sufficiently high catalytic activity and a narrow molecular weight distribution even in a small amount can be obtained. Further, by reacting two or more specific compounds (hereinafter also referred to as "modifiers") after the polymerization is completed, The present invention has been found to be able to suppress the cold flow, and to have excellent mechanical properties, workability and abrasion resistance of the obtained polymer, and have reached the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a conjugated diene system.
A catalyst comprising, as a main component, the following components (a) to (c):
After polymerization using, the following component (d) and
At least one selected from the group consisting of components (e) to (j)
(Hereinafter referred to as "denaturation").
Method for producing conjugated diene-based polymer characterized by that
About the law. (A) component: a rare element corresponding to atomic numbers 57 to 71 in the periodic table
Earth element-containing compounds, or these compounds and Lewis
Reaction product with base (b) component; alumoxane and / or AlR¹ R^Two 
R^Three (Where R¹ And R^Two Are the same or different, carbon
A hydrocarbon group or a hydrogen atom of the formulas 1 to 10, R^ThreeIs the carbon number
1 to 10 hydrocarbon groups, provided that R^Three Is R¹ 
Or R^Two May be the same or different)
Organoaluminum compound (c) component; halogen-containing compound (d) component; epoxy group and / or isocyanate
Alkoxysilation having at least one group in the molecule
Compound (e) component; R^Four _nM'X_4-n, M'X_Four , M'X_Three ,
R^Four _nM '(R^Five -COOR⁶ )_4-nOr R^Four _nM '
(R^Five -COR⁶ )_4-n(Where R^Four And R ^Five Are the same
Or differently, a hydrocarbon group having 1 to 20 carbon atoms, R⁶ Is charcoal
A hydrocarbon group having a prime number of 1 to 20, and a carbonyl group
Or an ester group may be contained, and M '
Atom, silicon atom, germanium atom or phosphorus atom, X
Is a halogen atom, and n is an integer of 0 to 3)
Metal halide compounds, metal halide compounds
Or an organometallic compound (f) component; in the molecule, a Y = C = Z bond (where Y is a carbon
Element atom, oxygen atom, nitrogen atom or sulfur atom, Z is oxygen
Atom, nitrogen atom or sulfur atom)
Lokumulene compound (g) component; in the molecule

[0009]

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A bond wherein Y is an oxygen atom, a nitrogen atom or
Is a sulfur atom).
However, the component (d) is excluded. (H) component; halogenated isocyano compound (i) component; R⁷ (COOH)_m, R⁸ (COX)_m,
R⁹ COO-R^Ten, R ¹¹-OCOO-R¹², R¹³(CO
OCO-R¹⁴)_mOr

[0011]

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Wherein R ^{7 to} R ¹⁵ are the same or different,
A hydrocarbon group having 1 to 50 carbon atoms, X is a halogen atom, and m is an integer of 1 to 5 corresponding to the group bonded to the hydrocarbon group), a carboxylic acid, an acid halide, an ester compound, Carbonic acid ester compound or acid anhydride (j) component: R ¹⁶ _l M ″ (OCOR ¹⁷ ) _4-l , R
¹⁸ _l M "(OCO-R ¹⁹ -COOR ²⁰ ) _4-l , or

[0013]

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(Wherein R ^{16 to} R ²² are the same or different,
A metal salt of a carboxylic acid corresponding to a hydrocarbon group having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and l is an integer of 0 to 3)

The component (b) is preferably a combination of alumoxane and an organoaluminum compound corresponding to AlR ¹ R ² R ³ (wherein R ^{1 to} R ³ are the same as above). Further, the halogen-containing compound as the component (c) is preferably a reaction product of a metal halide and a Lewis base. As the above metal halide, 1
It is preferable that the metal halide of the group 2, 2 and / or 7 and the Lewis base be a phosphate, a diketone compound, a carboxylic acid and / or an alcohol. Furthermore, a polymer obtained by polymerizing the conjugated diene compound using a catalyst having the above-mentioned components (a) to (c) as a main component has a cis-1,4-bond content of 90% or more and gel permeation. The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by chromatography is preferably 3.5 or less.
Further, the polymer obtained by reacting the component (d) in combination with at least one compound selected from the group consisting of the components (e) to (j) has a cis-1,4-bond content. It is preferable that the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 90% or more and 4 or less.

[0016]

DETAILED DESCRIPTION OF THE INVENTION (a) Used in the catalyst of the present invention
The component is a compound containing a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table (a compound containing a rare earth element) or a reaction product of these compounds with a Lewis base. Preferred rare earth elements are neodymium, praseodymium, cerium, lanthanum, gadolinium and the like, or a mixture thereof, and more preferably neodymium. The rare earth element-containing compound of the present invention is a carboxylate, an alkoxide, a β-diketone complex, a phosphate or a phosphite, among which a carboxylate or a phosphate is preferable, and a carboxylate is particularly preferable. .

The carboxylate of a rare earth element is represented by the general formula (R ²³ -CO ₂ ) ₃ M (where M is a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table).
²³ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a saturated or unsaturated alkyl group, and is linear, branched or cyclic, and the carboxyl group is a primary, secondary or tertiary. Attached to a carbon atom. Specifically, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [trade name of Shell Chemical Co., Ltd. Or a carboxylic acid bonded thereto], and the salts of 2-ethylhexanoic acid, naphthenic acid and versatic acid are preferred.

The rare earth alkoxide is represented by the general formula (R ²⁴ O) ₃ M (M is an atomic number 57 to 71 in the periodic table)
Examples of the alkoxy group represented by R ²⁴ O include a 2-ethyl-hexylalkoxy group, an oleylalkoxy group, a stearylalkoxy group, a phenoxy group, a benzylalkoxy group, and the like. Among them, preferred are a 2-ethyl-hexylalkoxy group and a benzylalkoxy group.

The β-diketone complex of a rare earth element includes
Rare earth elements such as acetylacetone, benzoylacetone, propionitrileacetone, valerylacetone, and ethylacetylacetone complex are exemplified. Among them, preferred are acetylacetone complex and ethylacetylacetone complex.

As the phosphate or phosphite of the rare earth element, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, bis (p-nonylphenyl) phosphate of the rare earth element can be used. Bis (polyethylene glycol-p-nonylphenyl) phosphate, (1-methylheptyl) phosphate (2-ethylhexyl), (2-ethylhexyl) phosphate (p-nonylphenyl), mono-2-ethylhexylphosphonate -Ethylhexyl, mono-p-nonylphenyl 2-ethylhexylphosphonate, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2-ethylhexyl) phosphinic acid, (2-ethylhexyl)
Salts such as (p-nonylphenyl) phosphinic acid are mentioned, and preferred examples are bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, Salts of bis (2-ethylhexyl) phosphinic acid are mentioned. Particularly preferred among the above examples are neodymium phosphate and neodymium carboxylate, and particularly preferred are carboxylate salts such as neodymium 2-ethylhexanoate and neodymium versatate.

The Lewis base used for easily solubilizing the above-mentioned compound containing a rare earth element in a solvent and for stably storing it for a long period of time contains 1 mole of a rare earth element per mole of the rare earth element.
It is used in a proportion of 0 to 30 mol, preferably 1 to 10 mol, as a mixture of both or as a product obtained by previously reacting both. Here, as the Lewis base,
For example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, a monohydric or dihydric alcohol can be used. The rare earth element-containing compounds (a) or the reaction products of these compounds with a Lewis base can be used alone or in combination of two or more.

Alumoxane, one of the components (b) used in the catalyst of the present invention, is a compound having a structure represented by the formula (I) or (II). Also, Fine Chemicals, 23, (9), 5 (1994); Am. Ch
em. Soc. , 115, 4971 (1993);
Am. Chem. Soc. , 117, 6465 (199
The alumoxane aggregate shown in 5) may be used.

[0023]

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[0024] (wherein, R ²⁵ is a hydrocarbon group having 1 to 20 carbon atoms, n 'is an integer of 2 or more.) In the alumoxane represented by the formula (I) or Formula (II), in R ²⁵ Examples of the hydrocarbon group represented include methyl, ethyl, propyl, butyl, isobutyl, t-butyl, hexyl, isohexyl, octyl, isooctyl group, and the like, preferably, methyl, ethyl, isobutyl,
It is a t-butyl group, particularly preferably a methyl group. N 'is an integer of 2 or more, preferably 4 to 100. (B) Specific examples of alumoxanes include methylalumoxane, ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, isohexylalumoxane, and the like. No.
(B) The production of alumoxane may be performed by any known technique. For example, trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, or xylene, and further contains water, water vapor, and water vapor. It can be produced by adding nitrogen gas or a salt having water of crystallization such as copper sulfate pentahydrate or aluminum sulfate 16 hydrate to cause a reaction.
(B) Alumoxane can be used alone or in combination of two or more.

The other component (b) used in the catalyst of the present invention, AlR ¹ R ² R ³ (wherein R ¹ and R ² are the same or different and have a hydrocarbon group of 1 to 10 carbon atoms or hydrogen) The atom and R ³ are a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ² ). , Triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, hydrogen Diethyl aluminum chloride,
Di-n-propylaluminum hydride, di-n-hydride
Butyl aluminum, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, dioctyl aluminum hydride, diisooctyl aluminum hydride, ethyl aluminum dihydride, n-propyl aluminum dihydride, isobutyl aluminum dihydride, etc. And preferably, triethylaluminum, triisobutylaluminum, diethylaluminum hydride,
Diisobutylaluminum hydride. The organoaluminum compound as the component (b) of the present invention can be used alone or in combination of two or more. The aluminoxane and the organoaluminum compound corresponding to AlR ¹ R ² R ³ which are the components (b) can be used alone or in combination, respectively. It is preferable to use them in combination.

The component (c) used in the catalyst of the present invention comprises:
It is a halogen-containing compound. As the halogen-containing compound (c), a halogenated organometallic compound or a metal halide compound having a chlorine atom, a bromine atom and / or an iodine atom (hereinafter, also referred to as “compound”),
A silicon halide compound and / or a halogenated organosilicon compound (hereinafter, also referred to as “compound”), and a reaction product of a metal halide and a Lewis base (hereinafter, “compound”)
A compound).

Among the components (c), the compound is a halogen compound containing a metal belonging to Group II, III, IV, V, VI, VII or VIII of the periodic table. A chlorine atom or a bromine atom is preferred.

These compounds include ethyl magnesium iodide, ethyl magnesium chloride,
Ethyl magnesium bromide, n-propyl magnesium chloride, n-propyl magnesium bromide, isopropyl magnesium chloride, isopropyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, n-butyl magnesium iodide, t-butyl magnesium chloride, t -Butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, Ethyl aluminum iodide, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum iodide, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, dibutyl tin dichloride, aluminum Trichloride, aluminum tribromide, aluminum triiodide, antimony trichloride, antimony pentachloride, phosphorus tribromide, phosphorus trichloride, phosphorus triiodide, phosphorus pentachloride, tin tetrabromide, tin tetrachloride, tetraiodide Titanium,
Titanium tetrachloride, tungsten hexachloride, magnesium (II) iodide anhydride, manganese pentacarbonyl bromide, manganese perchlorate (II) hexahydrate, manganese (II) chloride anhydrous, manganese (II) chloride Tetrahydrate, manganese (II) bromide anhydride, manganese (II) bromide ・ tetrahydrate, pentacarbonylrhenium bromide, pentacarbonylrhenium chloride, rhenium (III) chloride, rhenium (V) chloride, etc. Particularly preferred are diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide and the like.

The above-mentioned halogenated organic compound is a halogenated organic compound having a high reactivity with a base. Organochlorine compounds such as t-butyl chloride, chlorodiphenylmethane, chlorotriphenylmethane and methyl chloroformate; xylene dibromide, benzoyl bromide, propionyl bromide, benzyl bromide, benzylidene bromide, t-butyl bromide, methyl bromoformate Organic bromine compounds; benzoyl iodide,
Organic iodine compounds such as xylylene diiodide are exemplified.

Among the compounds, the silicon halide compounds include, for example, silicon tetrachloride, silicon tetrabromide,
Examples include silicon tetraiodide and hexachlorodisilane. Further, as the halogenated organosilicon compound, for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, triethylchlorosilane, trimethylchlorosilane, methylchlorosilane, trimethylbromosilane, diphenyldichlorosilane, dihexyldichlorosilane,
Dioctyldichlorosilane, dibutyldichlorosilane,
Diethyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, trichlorosilane, tribromosilane, vinylmethyldisilane Chlorosilane, vinyldimethylchlorosilane, chloromethylsilane, chloromethyltrimethylsilane, chloromethyldimethylchlorosilane, chloromethylmethyldichlorosilane, chloromethyltrichlorosilane, dichloromethylsilane, dichloromethylmethyldichlorosilane, dichloromethyldimethylchlorosilane, dichlorotetramethyldisilane , Tetrachlorodimethylsilane, bischlorodimethylsilylethane Dichloro tetramethyl disiloxane, trimethylsiloxy dichlorosilane, trimethylsiloxy dimethyl chlorosilane, and tris trimethylsiloxy dichlorosilane and the like. As the compound, preferably silicon tetrachloride, triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane,
Ethyltrichlorosilane, methyltrichlorosilane, trichlorosilane, dichlorotetramethyldisilane, dichlorotetramethyldisiloxane, and more preferably silicon tetrachloride.

Further, the compound is a reaction product of a metal halide and a Lewis base as described above. here,
Examples of the metal halide include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide, and barium iodide. , Zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, manganese bromide, manganese iodide, rhenium chloride, bromide Rhenium, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide and the like, preferably magnesium chloride,
Calcium chloride, barium chloride, manganese chloride, zinc chloride and copper chloride are preferred, and magnesium chloride, manganese chloride, zinc chloride and copper chloride are particularly preferred.

Further, as the Lewis base to be reacted to form a reaction product with the above-mentioned metal halide, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol and the like are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate,
Phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [manufactured by Shell Chemical Co., Ltd. Trade name, a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom], triethylamine,
N, N-dimethylacetamide, tetrahydrofuran,
Examples include diphenyl ether, 2-ethyl-hexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, and the like, and preferably tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, Ethylhexanoic acid, versatic acid, 2
-Ethylhexyl alcohol, 1-decanol, lauryl alcohol.

The Lewis base is used in an amount of 0.01 to 30 mol, preferably 0.1 to 30 mol, per 1 mol of the metal halide.
The reaction is performed at a ratio of 5 to 10 mol. Use of a reaction product with this Lewis base can reduce the amount of metal remaining in the polymer. The above compounds can be used alone or in combination of two or more.

The amount or composition ratio of each component of the catalyst used in the present invention is set to various different ones according to the purpose or necessity. Among them, the component (a) is 10
0.00001 to 0 g of the conjugated diene compound
It is preferred to use an amount of 1.0 mmol. 0.00001
If the amount is less than mmol, the polymerization activity is undesirably low,
On the other hand, if it exceeds 1.0 mmol, the catalyst concentration becomes high, and a deashing step is required, which is not preferable. In particular, 0.0
It is preferred to use an amount of 001 to 0.5 mmol. In general, the amount of the component (b) used can be represented by the molar ratio of Al to the component (a). : 3-1
750, more preferably 1: 5 to 1: 500.
Further, the ratio of the component (a) to the component (c) is a molar ratio,
1: 0.1 to 1:30, preferably 1: 0.2 to 1: 1
5 If the amount of the catalyst or the component ratio is out of the range, the catalyst does not act as a highly active catalyst, or a step of removing a catalyst residue is required. In addition to the components (a) to (c), a polymerization reaction may be performed in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.

As the catalyst component, the above-mentioned component (a),
In addition to the component (b) and the component (c), if necessary, a conjugated diene-based compound and / or a non-conjugated diene-based compound may be added in an amount of 0 to 1,000 per mole of the compound (a).
It may be used in a molar ratio. The conjugated diene-based compound used for the production of the catalyst, like the monomer for polymerization, 1,
3-butadiene, isoprene and the like can be used. Examples of the non-conjugated diene-based compound include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene. A conjugated diene-based compound as a catalyst component is not essential, but when used in combination, there is the advantage that the catalytic activity is further improved.

The catalyst is produced, for example, by reacting the components (a) to (c) dissolved in a solvent and, if necessary, a conjugated diene compound and / or a non-conjugated diene compound. At that time, the order of addition of each component may be arbitrary. These components are preferably mixed, reacted, and aged in advance from the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period. Here, the aging temperature is
It is 0-100 degreeC, Preferably it is 20-80 degreeC. If the temperature is lower than 0 ° C., aging is not sufficiently performed. On the other hand, if the temperature is higher than 100 ° C., the catalytic activity is reduced and the molecular weight distribution is undesirably widened. The aging time is not particularly limited, and it can be brought into contact in a line before adding to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient, and it is stable for several days.

In the present invention, the conjugated diene compound is polymerized using a catalyst containing the above components (a) to (c) as main components. Examples of the conjugated diene-based compound that can be polymerized with the catalyst of the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. , 1,3-hexadiene, myrcene, cyclo-1,3-pentadiene and the like, and particularly preferable are 1,3-butadiene, isoprene and 1,3-pentadiene. These conjugated diene compounds can be used alone or
A mixture of two or more species can be used. When two or more species are used in combination, a copolymer is obtained.

The polymerization of the conjugated diene polymer of the present invention can be carried out with or without a solvent. The polymerization solvent is an inert organic solvent, for example, 4-1 to 4 carbon atoms such as butane, pentane, hexane and heptane.
0 saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons having 6 to 20 carbon atoms such as cyclopentane and cyclohexane, 1-
Monoolefins such as butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene and bromobenzene And halogenated hydrocarbons such as chlorotoluene. These polymerization solvents can be used alone or in combination of two or more.

The polymerization temperature is usually from -30 ° C to 200 ° C,
Preferably it is 0-150 degreeC. The polymerization reaction may be either a batch type or a continuous type. Further, in order to prevent deactivation of the rare earth element compound-based catalyst of the present invention and the polymer in order to produce the polymer, mixing of a compound having a deactivating effect such as oxygen, water or carbon dioxide gas into the polymerization system is minimized. Care must be taken to eliminate them.

According to the present invention, since a specific catalyst is used, a conjugated diene polymer having a high cis-1,4-bond content and a sharp molecular weight distribution can be obtained.
As described above, the conjugated diene-based polymer obtained using the catalyst containing the components (a) to (c) as a main component is cis-1,4-
A bond content of 90% or more, preferably 93% or more;
w / Mn is at most 3.5, preferably at most 3.0, more preferably at most 2.5. When the cis-1,4-bond content of the conjugated diene polymer obtained in the present invention is less than 90%, mechanical properties and abrasion resistance are inferior. The adjustment of the cis-1,4-bond content can be easily performed by controlling the polymerization temperature. In the present invention, the conjugated diene polymer has a Mw / Mn of 3.5.
If it exceeds, mechanical properties and wear resistance are inferior. This Mw /
Adjustment of Mn can be easily performed by controlling the molar ratio of the above components (a) to (c).

The 1,2-vinyl bond content of the conjugated diene polymer is preferably 2.5% or less, and if it exceeds 2.5%, the mechanical properties and abrasion resistance are poor. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the conjugated diene polymer is as follows:
It is preferably in the range of 10 to 100. If it is less than 10, the mechanical properties after vulcanization, the abrasion resistance, etc. are inferior.
If it exceeds 100, workability at the time of kneading is inferior and mechanical properties are deteriorated.

Next, in the present invention, after the conjugated diene compound is polymerized using the rare earth element compound catalyst in this manner, a compound having a specific functional group at the active terminal of the obtained living polymer is successively added. By adding two or more of them in combination and reacting (modifying) the active terminal of the polymer with a compound having a specific functional group, a new polymer having an increased polymer molecular weight or a branched polymer chain is formed. Things. This modification improves abrasion resistance, mechanical properties, cold flow, especially cold flow.

In the present invention, the modifying agent to be reacted with the active terminal of the polymer essentially comprises the above component (d), and further comprises at least one component selected from the group consisting of the above components (e) to (j).
Use a combination of seeds. As a result, a conjugated diene-based polymer having further improved abrasion resistance, mechanical properties, and cold flow, particularly cold flow, can be obtained. This (d)
The component is an alkoxysilane compound having at least one epoxy group and / or isocyanate group in the molecule. Specific examples of the component (d) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltriphenoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane, ( 3-glycidyloxypropyl) methyldiethoxysilane,
(3-glycidyloxypropyl) methyldiphenoxysilane, condensate of (3-glycidyloxypropyl) methyldimethoxysilane, condensate of (3-glycidyloxypropyl) methyldiethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
Epoxy group-containing alkoxysilane compounds such as condensates of 3-glycidyloxypropyltrimethoxysilane and condensates of 3-glycidyloxypropyltriethoxysilane; 3-isocyanatopropyltrimethoxysilane;
3-isocyanatopropyltriethoxysilane, 3-
Isocyanatopropyltriphenoxysilane, (3-
Isocyanatopropyl) methyldimethoxysilane,
(3-isocyanatopropyl) methyldiethoxysilane, (3-isocyanatopropyl) methyldiphenoxysilane, condensate of (3-isocyanatopropyl) methyldimethoxysilane, (3-isocyanatopropyl) methyldiethoxysilane Contains isocyanate groups such as condensates, β-(... isocyanatocyclohexyl) ethyltrimethoxysilane, condensates of (3-isocyanatopropyl) trimethoxysilane, and condensates of (3-isocyanatopropyl) triethoxysilane An alkoxysilane compound is exemplified.

In the present invention, the halogenated organometallic compound or the metal halide compound as the component (e) to be reacted with the active terminal of the polymer is represented by the following formula (III). (Wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, M ′ is a tin atom, silicon atom, germanium atom or phosphorus atom, X is a halogen atom, and n is an integer of 0 to 3.) In (III), when M ′ is a tin atom, the component (e) includes, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride,
Diphenyltin dichloride, dibutyltin dichloride,
Examples include dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, and tin tetrachloride.

In the above formula (III), when M 'is a silicon atom, examples of the component (e) include triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, and diphenylchlorosilane. Examples include dichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenylchlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, and silicon tetrachloride.

In the above formula (III), when M 'is a germanium atom, the component (e) may be, for example, triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, butylgermanium trichloride, Further, when M ′ is a phosphorus atom in the formula (III), examples of the component (e) include phosphorus trichloride.

In the present invention, the component (e) is
And an ester group represented by the following formula (IV) or (V):
Or an organometallic compound containing a carbonyl group in the molecule.
Can also be used. R^Four _nM '(R^Five -COOR⁶ )_4-n... (IV) R^Four _nM '(R^Five -COR⁶ )_4-n ... (V) (where R^Four And R^Five Are the same or different and have 1 carbon atom
~ 20 hydrocarbon groups, R ⁶ Is a hydrocarbon having 1 to 20 carbon atoms
Group containing an ester group or a carbonyl group in the side chain
M ′ may be a tin atom, a silicon atom, a germanium
Um atom or phosphorus atom, and n is an integer of 0-3. ) These components (e) may be used in combination at any ratio.

The heterocumulene compound as the component (f) to be reacted with the active terminal of the polymer is a compound having a structure represented by the following formula (VI). Y = C = Z (VI) (wherein, Y is a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and Z is an oxygen atom, a nitrogen atom or a sulfur atom.) Here, the component (f) When Y is a carbon atom and Z is an oxygen atom, the compound is a ketene compound. When Y is a carbon atom and Z is a sulfur atom, the compound is a thioketene compound. When Y is a nitrogen atom and Z is an oxygen atom, A thioisocyanate compound when Y is a nitrogen atom and Z is a sulfur atom, a carbodiimide compound when Y and Z are both nitrogen atoms, and a carbon dioxide when Y and Z are both oxygen atoms. Carbon, Y is an oxygen atom, Z
Is a carbonyl sulfide when is a sulfur atom, Y and Z
Are carbon disulfide when both are sulfur atoms. However, the component (f) is not limited to these combinations.

Among them, examples of the ketene compound include ethyl ketene, butyl ketene, phenyl ketene, and toluyl ketene. Examples of the thioketene compound include ethylene thioketene, butyl thioketene, phenyl thioketene, and toluyl thioketene. Examples of the isocyanate compound include phenyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like. No. As the thioisocyanate compound, for example, phenylthioisocyanate, 2,2
4-tolylene dithio isocyanate, hexamethylene dithio isocyanate and the like. Examples of the carbodiimide compound include N, N'-diphenylcarbodiimide, N, N'-diethylcarbodiimide and the like.

The hetero three-membered ring compound which is the component (g) to be reacted with the active terminal of the polymer is a compound having a structure represented by the following formula (VII). However, the above component (d) is excluded.

[0051]

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(In the formula, Y is an oxygen atom, a nitrogen atom or a sulfur atom.) Here, among the components (g), for example, when Y is an oxygen atom, it is an epoxy compound, and In the case, it is an ethyleneimine derivative, and in the case of a sulfur atom, it is a thiirane compound. Here, as the epoxy compound, for example,
Ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl Ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, polypropylene glycol diglycidyl ether,
Polyethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycidyl methacrylate, glycidyl acrylate, N, N-diglycidyl aniline, N, N-diglycidyl toluidine, N, N-
Glycidylglycidyloxyaniline, tetraglycidylaminodiphenylmethane and the like can be mentioned. Further, as the ethyleneimine derivative, for example, ethyleneimine, propyleneimine, N-phenylethyleneimine,
N- (β-cyanoethyl) ethyleneimine and the like. Furthermore, examples of the thiirane compound include thiirane, methylthiirane, and phenylthiirane.

The halogenated isocyano compound as the component (h) to be reacted with the active terminal of the polymer is represented by the following formula (VIII)
Is a compound having a structure represented by As the halogenated isocyano compound as the component (h), for example, 2-amino-6-chloropyridine, 2,5
-Dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, 3,6-
Dichloro-4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6- Dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-
Chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4,5,6-tetrachloropyrimidine, 2,
4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6-dichloropyrazine, 2,4-bis (methylthio) -6-chloro-1,3,5-triazine, 2,4,6- Trichloro-1,3,5-triazine, 2-bromo-5-nitrothiazole, 2-chlorobenzothiazole, 2-chlorobenzoxazole and the like.

The carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride which is the component (i) to be reacted with the active terminal of the polymer is represented by the following formula (VI)
It is a compound having a structure represented by V) to (XIV). R ⁷ (COOH) _m・ ・ ・ (VIV) R ⁸ (COX) _m・ ・ ・ (X) R ⁹ COO-R ¹⁰・ ・ ・ (XI) R ¹¹ OCOO-R ¹²・ ・ ・ (XII) R ^{13 _{(COOCO-R 14) m ···}} (XIII)

[0055]

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Wherein R ^{7 to} R ¹⁵ are the same or different,
A hydrocarbon group having 1 to 50 carbon atoms, X is a halogen atom, and m is an integer of 1 to 5 corresponding to the group bonded to the hydrocarbon group. Here, in the component (i), examples of the carboxylic acid represented by the formula (VIV) include acetic acid, stearic acid, adipic acid, maleic acid, benzoic acid, acrylic acid, methacrylic acid, phthalic acid, and isophthalic acid. Acids, terephthalic acid, trimellitic acid, pyromellitic acid, melitic acid, polymethacrylic acid ester compounds or all or partial hydrolysates of polyacrylic acid compounds, and the like.

Examples of the acid halide represented by the formula (X) include acetic acid chloride, propionic acid chloride, butanoic acid chloride, isobutanoic acid chloride, octanoic acid chloride, acrylic acid chloride, benzoic acid chloride, stearic acid chloride, and the like. Examples include phthalic acid chloride, maleic acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, benzoyl fluoride and the like.

Examples of the ester compound represented by the formula (XI) include ethyl acetate, ethyl stearate, diethyl adipate, diethyl maleate, methyl benzoate,
Ethyl acrylate, ethyl methacrylate, diethyl phthalate, dimethyl terephthalate, tributyl trimellitate, tetraoctyl pyromellitate, hexaethyl melitate, phenyl acetate, polymethyl methacrylate,
Polyethyl acrylate, polyisobutyl acrylate, and the like, and examples of the carbonate compound represented by the formula (XII) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dihexyl carbonate, and diphenyl carbonate. Examples of the acid anhydride represented by the formula (XIII) include acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptanoic anhydride, benzoic anhydride, cinnamic anhydride, and the like. Examples of the acid anhydride represented by (XIV) include, for example, succinic anhydride, methylsuccinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, phthalic anhydride, styrene-maleic anhydride copolymer and the like. Can be

The compounds listed as component (i) may contain an aprotic polar group such as an ether group or a tertiary amino group in the coupling agent molecule as long as the object of the present invention is not impaired. It may be included. Also,
The component (i) may be used alone or
Mixtures of more than one species can be used. Further, (i)
The component may contain a compound containing a free alcohol group or a phenol group as an impurity.

The metal salt of carboxylic acid which is the component (j) to be reacted with the active terminal of the polymer is represented by the following formulas (XV) to (XVI)
Has the structure represented by

[0061]

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(Wherein R ^{16 to} R ²² are the same or different,
A hydrocarbon group having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and l is an integer of 0 to 3.)

Here, among the components (j), the above equation (XV)
Examples of the compound represented by are, for example, triphenyltin laurate, triphenyltin-2-ethylhexate, triphenyltin naphthate, triphenyltin acetate, triphenyltin acrylate, tri-n-
Butyltin laurate, tri-n-butyltin-2-ethylhexate, tri-n-butyltin naphthate,
Tri-n-butyltin acetate, tri-n-butyltin acrylate, tri-t-butyltin laurate, tri-t-butyltin-2-ethylhexate, tri-
t-butyltin naphthate, tri-t-butyltin acetate, tri-t-butyltin acrylate, triisobutyltin laurate, triisobutyltin-2-ethylhexate, triisobutyltin naphthate, triisobutyltin acetate, triisobutyltin Acrylate, triisopropyltin laurate, triisopropyltin-2-ethylhexate, triisopropyltin naphthate, triisopropyltin acetate,
Triisopropyltin acrylate, trihexyltin laurate, trihexyltin-2-ethylhexate, trihexyltin acetate, trihexyltin acrylate, trioctyltin laurate, trioctyltin-2-ethylhexate, trioctylsuzuna Phthate, trioctyltin acetate, trioctyltin acrylate, tri-2-ethylhexyltin laurate, tri-2-ethylhexyltin-2-ethylhexate, tri-2-ethylhexyltin naphthate, tri-2-ethylhexyltin Acetate, tri-
2-ethylhexyltin acrylate, tristearyltin laurate, tristearyltin-2-ethylhexate, tristearyltin naphthate, tristearyltin acetate, tristearyltin acrylate, tribenzyltin laurate, tribenzyltin-
2-ethyl hexatate, tribenzyl tin naphthate, tribenzyl tin acetate, tribenzyl tin acrylate, diphenyl tin dilaurate, diphenyl tin di-2-ethyl hexatate, diphenyl tin distearate, diphenyl tin dinaphthate, diphenyl tin diacetate, diphenyl tin Diacrylate,
Di-n-butyltin dilaurate, di-n-butyltin di-2-ethylhexate, di-n-butyltin distearate, di-n-butyltin dinaphthate, di-n
-Butyltin diacetate, di-n-butyltin diacrylate, di-t-butyltin dilaurate, di-t-
Butyltin di-2-ethylhexate, di-t-butyltin distearate, di-t-butyltin dinaphate, di-t-butyltin diacetate, di-t-butyltin diacrylate, diisobutyltin dilaurate,
Diisobutyltin di-2-ethylhexate, diisobutyltin distearate, diisobutyltin dinaphate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate,
Diisopropyltin-di-2-ethylhexate, diisopropyltin distearate, diisopropyltin dinaphthate, diisopropyltin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexate,
Dihexyltin distearate, dihexyltin dinaphate, dihexyltin diacetate, dihexyltin diacrylate, di-2-ethylhexyltin dilaurate, di-2-ethylhexyltin-di-2-ethylhexate, di-2-ethylhexyl Tin distearate, di-2-ethylhexyltin dinaphthate, di-2
-Ethylhexyltin diacetate, di-2-ethylhexyltin diacrylate, dioctyltin dilaurate, dioctyltin di-2-ethylhexate, dioctyltin distearate, dioctyltin dinaphate, dioctyltin diacetate, dioctyltin diacrylate , Distearyltin dilaurate, distearyltin di-2-ethylhexate, distearyltin distearate, distearyltin dinaphate, distearyltin diacetate, distearyltin diacrylate, dibenzyltin dilaurate, dibenzyltin di- 2-ethylhexate, dibenzyltin distearate, dibenzyltin dinaphthate, dibenzyltin diacetate, dibenzyltin diacrylate, phenyltin trilau Phenyltin triacetate, phenyltin triacetate, phenyltin triacrylate, n-butyltin trilaurate, n-butyltin tri-2-ethylhexate, n-butyltin triate Naphthate, n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate,
t-butyltin tri-2-ethylhexate, t-butyltin trinaphate, t-butyltin triacetate, t-butyltin triacrylate, isobutyltin trilaurate, isobutyltin tri-2-ethylhexate, isobutyltin trinaphate , Isobutyltin triacetate, isobutyltin triacrylate, isopropyltin trilaurate, isopropyltin tri-2-ethylhexate, isopropyltin trinaphate, isopropyltin triacetate, isopropyltin triacrylate, hexyltin trilaurate, hexyltin trilaurate -2-ethyl hexatate,
Hexyltin trinaphate, hexyltin triacetate, hexyltin triacrylate, octyltin trilaurate, octyltin tri-2-ethylhexate, octyltin trinaphate, octyltin triacetate, octyltin triacrylate, 2-ethylhexyltin Trilaurate, 2-ethylhexyltin tri-2-ethylhexate, 2-ethylhexyltin trinaphthate, 2-ethylhexyltin triacetate, 2-ethylhexyltin triacrylate, stearyltin trilaurate, stearyltin tri-2
-Ethyl hexatate, stearyl tin trinaphate, stearyl tin triacetate, stearyl tin triacrylate, benzyl tin trilaurate, benzyl tin tri-2-ethylhexate, benzyl tin trinaphate, benzyl tin triacetate, benzyl tin triacetate And the like.

The compounds represented by the above formula (XVI) include, for example, diphenyltin bismethylmalate, diphenyltinbis-2-ethylhexylmalate, diphenyltinbisoctylmalate, diphenyltinbisbenzylmalate, di-n -Butyltin bismethylmalate, di-n-butyltinbis-2-ethylhexylmalate, di-n-butyltinbisoctylmalate, di-n-butyltinbisbenzylmalate, di-t-butyltinbismethylmalate, Di-t-butyltin bis-
2-ethylhexylmalate, di-t-butyltin bisoctylmalate, di-t-butyltinbisbenzylmalate, diisobutyltinbismethylmalate, diisobutyltinbis-2-ethylhexylmalate, diisobutyltinbisoctylmalate, Diisobutyltin bisbenzylmalate, diisopropyltinbismethylmalate, diisopropyltinbis-2-ethylhexylmalate, diisopropyltinbisoctylmalate,
Diisopropyltin bisbenzyl malate, dihexyl tin bismethyl malate, dihexyl tin bis-2-ethylhexyl malate, dihexyl tin bisoctyl malate, dihexyl tin bisbenzyl malate, di-2
-Ethylhexyltin bismethylmalate, di-2-ethylhexyltin bis-2-ethylhexylmalate,
Di-2-ethylhexyltin bisoctyl malate, di-2-ethylhexyltin bisbenzyl malate, dioctyl tin bismethyl malate, dioctyl tin bis-
2-ethylhexyl malate, dioctyl tin bis octyl malate, dioctyl tin bis benzyl malate,
Distearyl tin bismethyl malate, distearyl tin bis-2-ethylhexyl malate, distearyl tin bisoctyl malate, distearyl tin bisbenzyl malate, dibenzyl tin bismethyl malate, dibenzyl tin bis-2- Ethylhexylmalate, dibenzyltin bisoctylmalate, dibenzyltinbisbenzylmalate, diphenyltinbismethyladipate, diphenyltinbis-2-ethylhexyladipate, diphenyltinbisoctyladipate, diphenyltinbisbenzyladipate, di-n-butyltinbismethyl Adipate, di-n-butyltin bis-2-ethylhexyl adipate, di-n-butyltin bisoctyl adipate, di-n-butyltin bisbenzyl adipate, di-t-butyl Dibutyltin bis-methyl adipate, di -t- Buchirusuzubisu-2-ethylhexyl adipate, di -t- butyl tin bis-octyl adipate, di -
t-butyltin bisbenzyl adipate, diisobutyltin bismethyl adipate, diisobutyltin bis-2
-Ethylhexyl adipate, diisobutyltin bisoctyl adipate, diisobutyltin bisbenzyl adipate, diisopropyltin bismethyl adipate, diisopropyltin bis-2-ethylhexyl adipate, diisopropyltin bisoctyl adipate, diisopropyltin bisbenzyl adipate, dihexyltin bismethyl adipate, dihexyl Tin bis-2-ethylhexyl adipate, dihexyl tin bismethyl adipate, dihexyl tin bisbenzyl adipate, di-2-ethylhexyl tin bismethyl adipate, di-
2-Ethylhexyltin bis-2-ethylhexyl adipate, di-2-ethylhexyltin bisoctyl adipate, di-2-ethylhexyltin bisbenzyl adipate, dioctyltin bismethyl adipate, dioctyltin bis-2-ethylhexyl adipate, dioctyltin bisoctyl Adipate, dioctyltin bisbenzyl adipate, distearyl tin bismethyl adipate, distearyl tin bis-2-ethylhexyl adipate, distearyl tin bisoctyl adipate,
Distearyl tin bisbenzyl adipate, dibenzyl tin bismethyl adipate, dibenzyl tin bis-2-
Ethylhexyl adipate, dibenzyltin bisoctyl adipate, dibenzyltin bisbenzyl adipate, etc., and compounds containing two carboxylic acid groups such as malonic acid, malic acid, succinic acid, etc. in place of the above maleic acid and adipic acid And the like.

Further, as the compound represented by the above formula (XVII), for example, diphenyltin maleate, di-n-butyltin maleate, di-t-butyltin maleate, diisobutyltin maleate, diisopropyltin maleate,
Dihexyl tin malate, di-2-ethylhexyl tin malate, dioctyl tin malate, distearyl tin malate, dibenzyl tin malate, diphenyl tin adipate, di-n-butyl tin adipate, di-t-butyl tin adipate, diisobutyl tin In addition to adipate, diisopropyltin adipate, dihexyltin diadipate, di-2-ethylhexyltin adipate, dioctyltin adipate, distearyl tin adipate, dibenzyltin adipate, etc. Derivatives of compounds containing two carboxylic acid groups such as malic acid and succinic acid are exemplified. The compounds of the above components (d) to (j) (hereinafter also referred to as "modifiers") can be used alone or in combination of two or more. In the present invention, the component (d) is indispensable as a modifier, and at least one compound selected from the group of components (e) to (j) is used in combination with the component, whereby the effect of the cold flow is further improved. Be improved. Particularly preferably, as a modifier, the combination of the component (d) with the component (f) or the component (j) further improves the cold flow. In the case of this combination, the order of addition is not particularly limited.

Here, the amount of the modifier to be used with respect to the above-mentioned component (a) is 0.01 to 200, preferably 0.1 to 150 in a molar ratio. On the other hand, the effect of improving wear resistance and cold flow is not exhibited. On the other hand, even when used in excess of 200, the effect of improving physical properties is saturated, and economically and sometimes, toluene-insoluble (Gel) is not preferred. Further, the component (d) and the other components [(e) to
(J) component], the component (d) is 5 to 90 mol%,
It is preferably from 10 to 80 mol%, and the other components are from 95 to 10 mol%, preferably from 90 to 20 mol%. When the amount of the component (d) is less than 5 mol% in the modifier, the effect of improving the cold flow is not exhibited.
Similarly, the effect of improving the cold flow is not exhibited. The above denaturation reaction is performed at 160 ° C. or lower, preferably at −30 ° C. to +
At a temperature of 130 ° C., 0.1 to 10 hours, preferably 0.1 to 10 hours.
It is desirable to carry out for 2 to 5 hours.

After the modification reaction of the target polymer is completed, if necessary, a polymerization terminator and a polymer stabilizer are added to the reaction system, and a known solvent removal and drying operation in the production of a conjugated diene polymer is performed. Can be recovered. The conjugated diene polymer obtained after the modification has a cis-1,4-bond content of 90% or more, preferably 93% or more, and a ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). ) Is 4 or less,
Preferably it is 3.5 or less. If the cis-1,4-bond content is less than 90%, the abrasion resistance is poor. Also, Mw / Mn
Exceeds 4, the wear resistance is poor. Incidentally, the vinyl-1,2-bond content of the obtained conjugated diene polymer was 2.5%.
% Or less, preferably 2.0% or less, and if it exceeds 2.5%, the durability is poor. The Mooney viscosity at 100 ° C. (ML _{1 + 4} , 100 ° C.) of the polymer is 10 to 10.
It is preferably in the range of 150. If it is less than 10, the abrasion resistance after vulcanization is inferior.
Poor workability during kneading. Further, the weight average molecular weight of the above polymer in terms of polystyrene is usually 100,000 to 150.
10,000, preferably 150,000 to 1,000,000. Outside these ranges, the processability and the physical properties of the vulcanized rubber are inferior and are not preferred. In addition, the obtained polymer, if necessary, before removing the solvent, aromatic oil, process oil such as naphthenic oil, per 100 parts by weight of the polymer, 5 to 5
After adding 100 parts by weight, it can be recovered by removing the solvent and drying.

The conjugated diene-based polymer obtained according to the present invention is blended with the polymer alone or with another synthetic rubber or natural rubber. If necessary, a process oil is blended. , Vulcanization by adding fillers such as carbon black, vulcanizing agents, vulcanization accelerators and other usual compounding agents, and treads and sidewalls for winter tires such as passenger car, truck, bus tires and studless tires It is used for rubber applications requiring mechanical properties and abrasion resistance, such as various members, hoses, belts, anti-vibration rubber, and various other industrial products. In addition, emulsion polymerization SBR other than natural rubber, solution polymerization SBR, polyisoprene, EP
(D) M, butyl rubber, hydrogenated BR, hydrogenated SBR can be blended and used.

As the vulcanizing agent, sulfur is usually used,
The amount used is 0.1 parts by weight based on 100 parts by weight of the raw rubber.
To 3 parts by weight, preferably 0.5 to 2 parts by weight. As the vulcanization aid and the processing aid, stearic acid is generally used, and its use amount is 0.5 to 5 parts by weight based on 100 parts by weight of the raw rubber. The vulcanization accelerator is not particularly limited, but is preferably M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide),
Thiazole vulcanization accelerators such as CZ (N-cyclohexyl-2-benzothiazylsulfenamide) can be used. Parts, preferably 0.2 to 3 parts by weight.

[0070]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are based on weight unless otherwise specified. Various measurements in the examples were performed by the following methods.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) was measured at a preheating time of 1 minute, a measuring time of 4 minutes, and a temperature of 100 ° C. Number average molecular weight (Mn), weight average molecular weight (Mw ) The measurement was performed using HLC-8120GPC manufactured by Tosoh Corporation under the following conditions using a differential refractometer as a detector. Column: Tosoh Corporation, column GMHHXL Mobile phase: tetrahydrofuran microstructure (cis-1,4-bond content, vinyl-1,2
-Bonding content ) It was determined by an infrared method (Morello method). Cold Flow (C / F) Measured by extruding the polymer through a 1/4 inch orifice at a pressure of 3.5 lb / in ² and a temperature of 50 ° C. After standing for 10 minutes, the extrusion speed was measured and the value was measured in milligrams per minute (mg / m
in).

The tensile strength was measured according to JIS K6301. Rebound Dunlop Ltd., using a rebound tester, to measure the value of at 50 ° C.. Using a wear-resistant Lambourn abrasion tester (manufactured by Shimada Giken Co., Ltd.)
The slip ratio was measured at room temperature at 60%.

Example 1 In a nitrogen-purged autoclave having an inner volume of 5 L, 2.4 kg of cyclohexane and 1,3-butadiene 3 were added under nitrogen.
00g was charged. Neodymium versatate (hereinafter referred to as “Nd (ver)”)
₃ ") (0.037 mmol) in cyclohexane, methylalumoxane (hereinafter also referred to as" MAO ") (2.22 mmol) in toluene, diisobutylaluminum hydride (hereinafter also referred to as" Al ⁱ Bu ₂ H "). (3.6 mmol) and a catalyst obtained by reacting a toluene solution (0.074 mol) of diethylaluminum chloride (hereinafter also referred to as "DEAC") with 1,3-butadiene, which is 5 times the amount of neodymium, at 50 ° C. for 30 minutes. At 80.degree. C. for 1 hour. The reaction conversion of 1,3-butadiene was almost 100%. Next, the temperature of the polymerization solution was maintained at 50 ° C., and 3-glycidyloxypropyltrimethoxysilane (hereinafter also referred to as “GPMOS”) (0.37 mmol) was added. After reacting for 10 minutes, dioctyltin bisoctylma A rate (hereinafter also referred to as “DOTBOM”) (0.19 mmol) was added, and the mixture was further reacted for 30 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added, and after terminating the polymerization, the solvent was removed by steam stripping, and the polymer was dried with a roll at 110 ° C. to obtain a polymer. Obtained. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 2 A polymer was obtained in the same manner as in Example 1, except that the order of addition of 3-glycidyloxypropyltrimethoxysilane and dioctyltin octylmalate was reversed. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 3 A polymer was obtained in the same manner as in Example 1 except that a mixed solution of 3-glycidyloxypropyltrimethoxysilane and dioctyltin octylmalate was used. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 4 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was used instead of diethylaluminum chloride. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 5 A polymer was obtained in the same manner as in Example 1, except that diethyl aluminum chloride was replaced with a complex of zinc chloride and tricresyl phosphate. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 6 Example 1 was repeated except that diethylaluminum chloride was replaced with a complex of zinc chloride and 1-decanol.
A polymer was obtained in the same manner as described above. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 7 Example 1 was repeated except that 3-glycidyloxypropyltrimethoxysilane was replaced by 3-isocyanatopropyltriethoxysilane (hereinafter also referred to as “IPMOS”).
A polymer was obtained in the same manner as in Example 1. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 8 A polymer was obtained in the same manner as in Example 1 except that dioctyltin octylmalate was changed to dioctyltin dichloride (hereinafter also referred to as "Oct ₂ SnCl ₂ "). Was. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 9 A polymer was prepared in the same manner as in Example 1 except that dioctyltin octyl malate was replaced with polymeric diphenylmethane diisocyanate (hereinafter also referred to as "MDI"). Obtained. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 10 In Example 1, dioctyltin octylmalate was replaced with trimethylolpropane polyglycidyl ether (hereinafter referred to as “TM
P)), except that the polymer was obtained in the same manner as in Example 1. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 11 A polymer was obtained in the same manner as in Example 1 except that dioctyltin octylmalate was replaced with diethyl adipate. Table 1 shows the polymerization conditions and the analysis results of the polymer.

Example 12 2.4 kg of cyclohexane and 1,3-butadiene 3 were placed in a nitrogen-purged autoclave having an inner volume of 5 L under nitrogen.
00g was charged. As a catalyst component, a solution of neodymium versatate (0.37 mmol) in cyclohexane, a solution of diisobutylaluminum hydride (14.8 mmol) in toluene and a solution of diethylaluminum chloride (0.74 mol) in toluene were prepared 5 times as much as neodymium. Amount of 1,3-butadiene and 3 at 50 ° C.
A catalyst aged for 0 minutes was charged, and polymerization was carried out at 80 ° C. for 1 hour. The reaction conversion of 1,3-butadiene was almost 100%. Next, the temperature of the polymerization solution was kept at 50 ° C., 3-glycidyloxypropyltrimethoxysilane (1.9 mmol) was added, and the mixture was reacted for 10 minutes.
ol) and reacted for an additional 30 minutes. afterwards,
A methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added, and after terminating the polymerization, the solvent was removed by steam stripping and dried with a roll at 110 ° C. to obtain a polymer. . Table 1 shows the polymerization conditions and the analysis results of the polymer.

COMPARATIVE EXAMPLE 1 In a 5-liter autoclave purged with nitrogen, 2.4 kg of cyclohexane and 300 g of 1,3-butadiene were charged under nitrogen. A cyclohexane solution of neodymium versatate (0.037 mmol) as a catalyst component and methylalumoxane (2.22 m
mol) of toluene solution, diisobutylaluminum hydride (3.6 mmol) and a toluene solution of a complex of zinc chloride and 1-decanol (0.074 mmol) with 1,3-butadiene five times the amount of neodymium at 50 ° C. for 30 minutes. A catalyst which had been aged for a minute was charged and polymerization was carried out at 80 ° C for 60 minutes. The polymerization conversion of 1,3-butadiene is approximately 1
00%. To this polymerization solution, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added, and after terminating the polymerization, the solvent was removed by steam stripping and dried with a roll at 110 ° C. A polymer was obtained.
Table 1 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 2 2.4 kg of cyclohexane and 300 g of 1,3-butadiene were charged under nitrogen into an autoclave having an internal volume of 5 liters and purged with nitrogen. A cyclohexane solution of neodymium versatate (0.037 mmol) as a catalyst component and methylalumoxane (2.22 m
mol) in toluene, diisobutylaluminum hydride (3.6 mmol) and diethylaluminum chloride in toluene (0.074 mmol) were reacted with 1,3-butadiene in an amount 5 times the amount of neodymium at 50 ° C. for 30 minutes. And polymerized at 80 ° C. for 60 minutes. The polymerization conversion of 1,3-butadiene is approximately 100
%Met. Next, while maintaining the temperature of the polymerization solution at 50 ° C.,
Glycidyloxypropyltrimethoxysilane [trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.] (0.3
7 mmol) and reacted for 30 minutes. afterwards,
A methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added, and after terminating the polymerization, the solvent was removed by steam stripping and dried with a roll at 110 ° C. to obtain a polymer. . Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 3 A polymer was obtained in the same manner as in Comparative Example 2 except that 3-glycidyloxypropyltrimethoxysilane was replaced with 3-isocyanatopropyltrimethoxysilane. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 4 A polymer was obtained in the same manner as in Comparative Example 2, except that 3-glycidyloxypropyltrimethoxysilane was changed to dioctyltin bisoctylmalate. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 5 A polymer was obtained in the same manner as in Comparative Example 2, except that 3-glycidyloxypropyltrimethoxysilane was changed to dioctyltin chloride. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 6 A polymer was obtained in the same manner as in Comparative Example 2 except that MDI was used instead of 3-glycidyloxypropyltrimethoxysilane. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 7 A polymer was obtained in the same manner as in Comparative Example 2, except that TMP was used instead of 3-glycidyloxypropyltrimethoxysilane. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 8 A polymer was obtained in the same manner as in Comparative Example 2, except that 3-glycidyloxypropyltrimethoxysilane was replaced with diethyl adipate. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 9 A polymer was obtained in the same manner as in Example 12, except that dioctyltin bisoctylmalate was not added. Table 2 shows the polymerization conditions and the analysis results of the polymer.

Comparative Example 10 Commercially available polybutadiene rubber [JR Co., Ltd.
Table 2 shows the vulcanization properties of Polybutadiene Rubber BR01].

Examples 1 to 12 show that the cold flow is improved as compared with Comparative Examples 1 to 10, and that the products modified with two kinds of modifiers are superior to the products modified alone.
Examples 1 to 3 also show that the order of addition does not affect the molecular weight distribution, microstructure, and cold flow.

Further, Examples 1 to 12 and Comparative Examples 1 to 1
Kneading and kneading were carried out using a plastmill according to the following formulation using the polymer No. 0 (polymer). Press vulcanization was performed at 145 ° C. for an optimum time to obtain a vulcanized test piece. Formulation (parts) Polymer 60 Natural rubber 40 HAF carbon black 50 Zinc white 3 Stearic acid 2 Antioxidant (* 1) 1 Vulcanization accelerator (* 2) 0.8 Sulfur 1.5 * 1) N-isopropyl- N'-phenyl-p-phenylenediamine * 2) N-cyclohexyl-2-benzothiazylsulfenamide

[0097]

[Table 1]

[0098]

[Table 2]

* 1) Ratio between weight average molecular weight (Mw) and number average molecular weight (Mn) * 2) The smaller the value, the better the storage stability. * 3) The polybutadiene rubber BR01 of Comparative Example 10
0, the larger the numerical value, the better the abrasion resistance. The rubber composition with carbon black using Examples 1 to 12 is different from Comparative Examples 1 to 10 in the breaking strength after vulcanization, the rebound resilience and the abrasion resistance. It can be seen that the properties are improved and it is useful to use two types of modifiers.

[0100]

According to the novel polymerization method of the present invention, the catalyst system used exhibits high polymerization activity with respect to conjugated diene compounds, and the obtained polymer has a narrow molecular weight distribution. Excellent characteristics. Moreover,
In the polymerization method of the present invention, following the above polymerization, the active end of the obtained polymer is reacted with a specific modifier in a combination of two or more kinds, so that cold flow, fracture characteristics, low heat generation, and abrasion resistance are achieved. Can be improved.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 9/00 C08L 9/00 (72) Inventor Shuji Nishihata 2-1-2-11 Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Iwawa Hattori 2--11-11 Tsukiji, Chuo-ku, Tokyo FSR term (reference) 4J002 AC021 AC031 AC051 AC061 DA036 GM00 GM01 GN00 GN01 GR00 4J015 DA37 4J100 AS01P AS02P AS03P AS04P BA02H BA12H BA15H BA16H BA20H BA29H BA42H BA46H BA51H BA54H BA77H BA93H BA94H BC04H BC43H BC54H BC65H BC73H BC75H BC80H BC83H CA01 CA15 CA31 DA04 DA47 FA08 HA35 HB57 HC08 HC25 HC27 HC28 HC29 HC30 HC33 HC39 HC78 HC51 HC

Claims (7)

[Claims] 1. The conjugated diene-based compound is represented by the following (a) to
(C) After polymerization using a catalyst containing the component as a main component,
Subsequently, the following component (d) and the following components (e) to (j)
Combination with at least one compound selected from the group
Of a conjugated diene polymer characterized by reacting
Construction method. (A) component: a rare element corresponding to atomic numbers 57 to 71 in the periodic table
Earth element-containing compounds, or these compounds and Lewis
Reaction product with base (b) component; alumoxane and / or AlR¹ R^Two 
R^Three (Where R¹ And R^Two Are the same or different, carbon
A hydrocarbon group or a hydrogen atom of the formulas 1 to 10, R^ThreeIs the carbon number
1 to 10 hydrocarbon groups, provided that R^Three Is R¹ 
Or R^Two May be the same or different)
Organoaluminum compound (c) component; halogen-containing compound (d) component; epoxy group and / or isocyanate
Alkoxysilation having at least one group in the molecule
Compound (e) component; R^Four _nM'X_4-n, M'X_Four , M'X_Three ,
R^Four _nM '(R^Five -COOR⁶ )_4-nOr R^Four _nM '
(R^Five -COR⁶ )_4-n(Where R^Four And R ^Five Are the same
Or differently, a hydrocarbon group having 1 to 20 carbon atoms, R⁶ Is charcoal
A hydrocarbon group having a prime number of 1 to 20, and a carbonyl group
Or an ester group may be contained, and M '
Atom, silicon atom, germanium atom or phosphorus atom, X
Is a halogen atom, and n is an integer of 0 to 3)
Metal halide compounds, metal halide compounds
Or an organometallic compound (f) component; in the molecule, a Y = C = Z bond (where Y is a carbon
Element atom, oxygen atom, nitrogen atom or sulfur atom, Z is oxygen
Atom, nitrogen atom or sulfur atom)
Lokumulene compound (g) component; in the moleculeA bond wherein Y is an oxygen, nitrogen or sulfur atom
3) heterocyclic ring compound (provided that
(D) Excluding the component. (H) component; halogenated isocyano compound (i) component; R⁷ (COOH)_m, R⁸ (COX)_m,
R⁹ COO-R^Ten, R ¹¹-OCOO-R¹², R¹³(CO
OCO-R¹⁴)_mOr(Where R⁷ ~ R^FifteenAre the same or different and have 1 to 5 carbon atoms
0 hydrocarbon group, X is a halogen atom, m is the above hydrocarbon
Corresponding to an integer of 1 to 5 corresponding to the group bonded to the group)
Carboxylic acid, acid halide, ester compound,
Carbonic acid ester compound or acid anhydride (j) component; R¹⁶ _lM "(OCOR¹⁷)_4-l, R
¹⁸ _lM "(OCO-R¹⁹-COOR²⁰)_4-lOr(Where R¹⁶~ R^{twenty two}Are the same or different and have 1 to 2 carbon atoms
0 is a hydrocarbon group, M ″ is a tin atom, a silicon atom or a
Rumanium atom, l is an integer from 0 to 3)
Metal salts of carboxylic acids 2. An alumoxane and Al as the component (b).
An organic aluminum compound corresponding to R ¹ R ² R ³ (wherein R ^{1 to} R ³ are the same as in claim 1) is used in combination.
A method for producing the conjugated diene-based polymer according to the above. 3. The halogen-containing compound as the component (c) is a reaction product of a metal halide and a Lewis base.
A method for producing the conjugated diene-based polymer according to the above. 4. The method according to claim 1, wherein the metal halide is of Group 1 or 2, and / or
4. The method for producing a conjugated diene polymer according to claim 3, wherein the conjugated diene-based polymer is a metal halide of Group 7 and the Lewis base is a phosphoric acid ester, a diketone compound, a carboxylic acid and / or an alcohol. 5. The conjugated diene compound according to the above (a) to
(C) A polymer obtained by polymerization using a catalyst having a component as a main component has a cis-1,4-bond content of 90% or more and a weight average molecular weight (Mw) and a number measured by gel permeation chromatography. Ratio to average molecular weight (Mn) (Mw
The method for producing a conjugated diene-based polymer according to claim 1, wherein (/ Mn) is 3.5 or less. 6. A polymer obtained by reacting the component (d) in combination with at least one compound selected from the group consisting of the components (e) to (j) to obtain cis-1,4- The bond content is 90% or more, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 4 or less. A method for producing the conjugated diene-based polymer according to the above. 7. A rubber composition comprising a conjugated diene-based polymer obtained by the method for producing a conjugated diene-based polymer according to claim 1 and carbon black.