JPS63178102A - Preparation of conjugated diene polymer - Google Patents

Abstract

PURPOSE:To obtain a conjugated diene polymer with its abrasion resistance, flexing resistance and low heat build-up property improved simultaneously, by polymerizing a conjugated diene in the presence of a lanthanide rare earth metal catalyst and reacting a specified organometallic halide with the polymer immediately after the polymerization. CONSTITUTION:A conjugated diene is polymerized in the presence of a catalyst consisting of ingredients (a) and (b) and, if necessary, containing ingredients (c) and/or (d) in an inert organic solvent, and the resulting polymer is reacted with ingredient (e), wherein (a) is a lanthanide rare earth element compound of formula LnY3 (where Ln is a metal having an atomic no. of 57-71; Y is -R, -OR, -SR, -NR2, X or RCOO-, R is a 1-20C hydrocarbon group; X is a halogen atom), (b) is an organoaluminum compound of formula AlR<1>R<2>R<3> (where R<1>-R<3> are the same as or different from each other, H, a 1-8C hydrocarbon group, not all of which are H simultaneously, (c) is a Lewis acid, (d) is a Lewis base, and (e) is an organometallic halide of formula Rn'MX4-n (where R' is a 1-20C alkyl group or an aryl group; M is a tin or germanium atom; X is a halogen atom; n is 1-3).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention involves polymerizing a conjugated diene using a lanthanum series rare earth metal catalyst, and reacting a specific halogenated organic metal with the polymer immediately after polymerization. The present invention relates to a method for producing a novel conjugated diene polymer having excellent wear resistance.

[Conventional technology]

In recent years, there has been an increasing demand for durability and long life for rubber members, and it has become important to improve the properties of rubber such as abrasion resistance, bending resistance, and low heat build-up.

Polybutadiene has hitherto been known as a rubber-like polymer with excellent wear resistance.
Polybutadiene produced using the lanthanum series rare earth metal catalyst proposed in Japanese Patent No. 57410 has particularly excellent wear resistance.

In addition, JP-A No. 60-40109 discloses that polybutadiene produced using a lanthanum series rare earth metal catalyst is reacted with tetrahalomethane or a specific organoaluminum compound to improve wear resistance and processability. It is stated that polybutadiene with excellent properties can be obtained.

[Problems to be Solved by the Invention] However, these known polybutadienes are still insufficient to simultaneously satisfy the various rubber properties described above.

The present invention was made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a conjugated diene polymer that simultaneously satisfies wear resistance, bending resistance, and low heat build-up.

[Means for solving problems]

That is, the present invention provides (a) (a) general formula LnYz (wherein Ln is a metal with an atomic number of 57 to 71 in the periodic table, and Y is -R, =OR, -3R, -NR1, or R.C.
OO-, where R is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom), and (b) a lanthanum series rare earth element compound represented by the general formula AIR'R''
R3 (herein, R'%R2 and R3 are the same or different and are hydrogen atoms or hydrocarbon groups having 1 to 8 carbon atoms, and are not all hydrogen atoms), and optionally Accordingly, the polymer obtained by polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst containing (c) a Lewis acid and/or +d) a Lewis base has (b) a general formula R'nMX, -, l (wherein, R'
is an alkyl group or aryl group having 1 to 20 carbon atoms, M is a tin atom or germanium atom, X is a halogen atom, and n is an integer of 1 to 3). The present invention provides a method for producing a conjugated diene polymer characterized by the following.

In the present invention, when obtaining a conjugated diene-based polymer such as polybutadiene, the polymer immediately after polymerization using a lanthanum series rare earth metal catalyst system is reacted with a specific halogenated organic metal, thereby improving wear resistance, low heat generation, etc. This is a further improvement in the initial characteristics.

The lanthanum series rare earth metal catalyst used in the present invention is (
a) a lanthanum series rare earth metal compound represented by the general formula LnY (hereinafter referred to as "component (a)"); and (b) an organoaluminum compound represented by the general formula AIR'R"R' (hereinafter referred to as r It is a catalyst system consisting of component (b). This can be done as needed (c1 the Lewis acid (
(hereinafter referred to as "component (c)") and/or the above (dl
It can contain a Lewis base (hereinafter referred to as "component (d)").

First, (in the Al component, Ln is a lanthanum series rare earth element with an atomic number of 57 to 71 in the periodic table, and among them, cerium, lanthanum, praseodymium, neodymium, and gadolinium are preferable, and neodymium is particularly easily available industrially. Therefore, it is preferable.

These rare earth elements may be a mixture of two or more.

Further, Y is in the form of alkoxide, thioalkoxide, amide, halogen and carboxylate,
Particularly preferred are alkoxides, halides, and carboxylates.

As carboxylates of rare earth elements, the general formula (RCOO
)s Ln, where R is a hydrocarbon group having 1 to 20 carbon atoms, preferably a saturated or unsaturated alkyl group, and is linear, branched or cyclic,
A carboxyl group is one bonded to a primary, secondary or tertiary carbon atom. Specifically, examples of preferred carboxylic acids include octanoic acid, 2-ethyl-hexanoic acid, oleic acid, stearic acid, benzoic acid, and naphthenic acid.

The alcohol type compound (alkoxide) is represented by the general formula Ln (OR):l (wherein Ln and R are the same as above), and the preferable alcohol is 2-
Examples include ethyl-hexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, and benzyl alcohol.

The thioalcohol type compound (thioalkoxide) is represented by the general formula Ln (SR):l (wherein Ln and R are the same as above), and a preferable thioalcohol is thiophenol.

As an amide type compound (amide), the general formula Ln (N
Rt ) s (in the formula, Ln and R are the same as above)
Preferred amines include dioctylamine,
Dioctylamine is mentioned.

Specific examples of these components (a) include neodymium trichloride, diditrichloride, 2-ethyl Hexanoic acid/neodymium, 2
- Ethylhexanoic acid/didimium, naphthenic acid/neodymium,
Examples include 2.2-diethylhexanoic acid and neodymium.

The organoaluminum compound as component (b) has the general formula AIR'R'' R3 (where Rt, Rz and R
3 is the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, but not all hydrogen atoms, specifically trimethylaluminum,
Triethyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, ethyl aluminum sibide, propyl aluminum sibide, isobutyl aluminum sibide, etc. can be mentioned.

As the Lewis acid which is the component (c), for example, general formula AI
An aluminum halide compound represented by R', x, l-wa (in the formula, R4 is a hydrocarbon group having 1 to 8 carbon atoms, m is an integer of O to 3, and X is the same as above), a halogen element, and Examples include halides such as tin and titanium.

Among these, particularly preferred are dimethylaluminum chloride, diethylaluminum chloride, diptylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and bromide and iodide compounds thereof.

+d) The Lewis base that is the component includes acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether,
Examples include triethylamine, organic phosphorus compounds, and monohydric or dihydric alcohols.

The composition of the lanthanum series rare earth metal catalyst used in the present invention is usually as follows.

(b) component/(a) component (molar ratio) is 10 to 150,
Preferably it is 15 to 100; if it is less than 10, the polymerization activity is low, while if it exceeds 150, there is little effect on the polymerization activity, which is economically disadvantageous.

In addition, component (c)/component (a) (molar ratio) is 0 to 6,
Preferably it is 0.5 to 5.0, and if it exceeds 6, the polymerization activity will decrease.

Furthermore, (dl component/(a) component (molar ratio) is 0 to 2
It is 0, preferably 1 to 15, and if it exceeds 20, the polymerization activity decreases, which is not preferable.

As a catalyst component, the above (al, (b), (c), (d)
In addition to the ingredients, if necessary, conjugated diene (0 to 1 mole of lanthanum series rare earth element compound, which is the al component)
It may be used in a proportion of 50 moles. The conjugated diene used for catalyst preparation is the same isoprene as the monomer for polymerization, 1.3
-butadiene, 1,3-pentadiene, etc. are used. Although the conjugated diene is not essential as a catalyst component, the catalytic activity of the catalyst component is further improved by using it in combination.

To prepare the catalyst, for example, (a) to (
It consists of reacting component d) and, if necessary, a conjugated diene. At that time, the order of addition of each component may be arbitrary. It is preferable to mix, react, and age each of these components in advance in order to improve polymerization activity and shorten the polymerization initiation induction period. good.

Examples of polymerization solvents include inert organic solvents, such as aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-butane, and cyclohexane, and methyl cyclohexane. Alicyclic hydrocarbon solvents such as pentane and cyclohexane, halogenated hydrocarbon solvents such as ethylene dichloride and chlorobenzene, and mixtures thereof can be used.

The polymerization temperature is usually -20°C to 150°C, preferably 30 to 120°C. The polymerization reaction may be carried out batchwise or continuously.

Note that the monomer concentration in the solvent is usually 5 to 50% by weight,
Preferably it is 10 to 35% by weight.

In addition, in order to prevent deactivation of the lanthanum series rare earth metal catalyst and living polymer of the present invention in order to produce a living polymer, it is necessary to avoid mixing compounds with a deactivation effect such as oxygen, water, or carbon dioxide gas into the polymerization system as much as possible. Consideration must be taken to eliminate this problem.

In addition, the conjugated dienes that can be polymerized with the catalyst of the present invention include:
Isoprene, 1,3-butadiene, 2゜3-dimethyl-
There are 1,3-butadiene, 1,3-pentadiene, etc., and they can be used alone or in combination of two or more kinds, especially 1.
3-Butadiene is preferred.

In the present invention, a conjugated diene is polymerized in an inert organic solvent using a lanthanum series rare earth metal catalyst, and then a specific halogenated organometallic is reacted with the active end of the living polymer obtained. A novel polymer having a tin-carbon bond or a germanium-carbon bond is formed by coupling three molecules of the pasting polymer.

This modification provides an effect of improving wear resistance.

In the present invention, the halogenated organic metal to be reacted with the living polymer is represented by the following general formula.

R'nMX4, (wherein R' is an alkyl group or aryl group having 1 to 20 carbon atoms, M is a tin atom or a germanium atom, X is the same as above, and n is an integer of 1 to 3; “(e)
Here, when M is a tin atom, component (8) is, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, diphenyltin chloride, dioctyltin dichloride, dibutyltin dichloride, phenyltin trichloride. Examples include chloride and butyltin trichloride.

Further, when M is a germanium atom, examples of the component (e) include compounds such as triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, and butylgermanium trichloride.

These components (e) may be used together in any proportion.

The amount of component (61) used relative to component (a) is component (e)/component (a) (molar ratio) = 0.1 to 100, more preferably 0.5 to 50, and less than 0.1 will cause reaction. The progress of the process is not sufficient, and the wear resistance improvement effect is poor, while 1
If it exceeds 0.00, it is unnecessary and undesirable as it may generate toluene insoluble matter (gel).

This campling reaction is carried out at 160°C or lower, preferably at 0.
It is advisable to carry out the reaction at a temperature of -130° C. under stirring for 0.1 to 10 hours, preferably 0.2 to 5 hours.

After the reaction is complete, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to solidify the modified polymer, and then the polymer is obtained by drying with a hot roll or under reduced pressure. be able to. Alternatively, the polymer can be obtained by directly removing the solvent from the polymer solution under reduced pressure.

The polymer obtained in the present invention is a high-cis 1゜4-diene polymer, and in the case of polybutadiene, the cis-
The amount of 1,4-coupled gold is 70% or more, preferably 80% or more. In addition, in the case of polyisoprene, cis-1,4
The amount of bonded metal is 88% or more, and the Mooney viscosity (MLl,
4.100℃) is 10-120, preferably 20-90
It is.

Furthermore, the high cis 1,4-butadiene-isoprene copolymer has a butadiene unit with a cis-1゜4 bond amount of 8.
0% or more, and cis-1 of the isoprene unit,
4. The amount of bonded metal is 88% or more. The composition of butadiene and isoprene in the copolymer at this time can be arbitrarily selected.

Furthermore, although the molecular weight of the polymer obtained in the present invention can be varied over a wide range, its Mooney viscosity (ML, at 100°C) is usually 10 to 120,
Preferably it is in the range of 15-100.

Furthermore, when the polymer obtained in the present invention is a copolymer, it can be obtained as a block copolymer or a random copolymer according to the structure of the living polymer.

Furthermore, the polymer of the present invention shows, for example, an infrared absorption spectrum that shows absorption around 700 cm-' due to Sn-φ bonds and absorption around 770 cm-' due to 5n-CHz bonds.
Its structure can be confirmed by nearby absorption.

On the other hand, when diphenyltin dichloride is used as component (e), the FourierTransform Spectrometer (FourierTrans
form NMR Spectrometer; hereinafter referred to as r
FT-NMRJ) using tetramethylsilane as a standard substance, δ = 7.4 pp due to Sn-φ bond.
The structure can be confirmed by the peak near m.

In addition, gel permeation chromatography (
The molecular weight distribution of polybutadiene without component (e) cannot be measured using a 254 nm ultraviolet detector in GPC) analysis. However, when diphenyltin dichloride is used as the [el component, the molecular weight distribution determined by ultraviolet rays and the molecular weight distribution determined by a differential refractometer are determined in correspondence due to the existence of Sn-φ bonds.

Thus, the polymer of the present invention may be used alone or in a blend with natural rubber and/or synthetic rubber other than the conjugated diene polymer of the present invention (hereinafter referred to as "other synthetic rubber").

Here, other synthetic rubbers include, for example, cis-1,4-
Including polyisoprene, emulsion polymerization styrene-butadiene copolymer, solution polymerization styrene-butadiene copolymer,
Examples include low cis-1,4-polybutadiene, high cis-1,4-polybutadiene, ethylene-propylene-diene copolymer, chloroprene, halogenated butyl rubber, and NBR.

Furthermore, the conjugated diene polymer of the present invention may include natural rubber and/or
Or when blending with other synthetic rubbers,
The proportion of the polymer of the present invention used is 20% by weight or more in the total rubber component, preferably 20 to 90% by weight of the polymer of the present invention,
80-10% by weight of natural rubber and/or other synthetic rubber
Therefore, if the amount of the polymer of the present invention is less than 20% by weight, the effect of the present invention cannot be achieved.

The conjugated diene polymer of the present invention is further extended with an aromatic, naphthenic, or paraffinic oil if necessary, and then fillers such as carbon black, silica, magnesium carbonate, calcium carbonate, glass fiber, etc. A composition can be prepared by adding conventional vulcanized rubber compounding agents such as stearic acid, zinc white, anti-aging agents, vulcanization accelerators, and vulcanizing agents.

After molding, the resulting composition is vulcanized and used for tire applications such as treads, undertreads, carcass, sidewalls, bead parts, hoses, belts, etc.
It can be used for shoe soles, window frames, sealants, and other industrial products.

〔Example〕

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 as long as the gist thereof is not exceeded.

In the examples, parts and % mean parts by weight and % by weight unless otherwise specified. Moreover, various measurements in the examples were based on the following methods.

The reaction between the active polymer and the halogenated organic metal immediately after polymerization using a lanthanum-based rare earth metal catalyst is confirmed by FT-NMR by observing the change in Mooney viscosity before and after the reaction, or by performing a model reaction with a polymerization average molecular weight of several thousand. Ta.

Mooney viscosity was measured at a temperature of 100° C. after 1 minute of preheating and 4 minutes of measurement (according to JIS K6300).

The microstructure of the polymer was determined by infrared absorption spectroscopy (Morello method).

Using the polymer of the present invention, according to the formulation shown below,
After kneading and blending using a 230 cc Brabender and a 6-inch roll, various measurements were performed using the vulcanized product, which was vulcanized at 145° C. for a predetermined period of time.

Compounding prescription (part) Polymer
100 carbon black (HAF
) 50 zinc white
3 Stearic acid 2 Anti-aging agent (810NA) 1 Vulcanization accelerator (T
P)” 0.8 vulcanization accelerator (MSA)
” 1 sulfur
1.5*1) N-phenyl-N'-isopropyl-p-phenylenediamine*2) Sodium diptyldithiocarbamate*3) N-
Oxydiethylene-2-benzothiazolesulfenamide vulcanization physical properties were measured according to JTS K6301.

The abrasion test was based on ASTM D2228 (Pico method). Here, the pico wear index is the emulsion polymerized styrene
The amount of wear of a vulcanized product of butadiene copolymer (#1500) was determined by the Pico method using a standard index of 100. The larger the index, the better the wear resistance. In addition, Pico wear index■
is polybutadiene rubber (Japan Synthetic Rubber ■, JSRBR
The wear amount of a vulcanizate of a rubber composition containing 50% of each of O1) and natural rubber was determined by the Pico method using a reference index of 100. The larger the index, the better the wear resistance.

As an index of exothermicity, rebound resilience (%) by Dunlop rebound test was used. This measurement method uses B5903
According to. The larger the 18 elasticity (%), the less heat generation and the better the result.

Example 1 After charging 2.5 kg of cyclohexane and 500 g of 1,3-butadiene in a reactor with an internal volume of 51 and equipped with a stirrer under a nitrogen atmosphere, (a) 2-ethyl was added in advance in the presence of 4.6 mmol of 1,3-butadiene. Neodymium hexanoate 0.
93 mmol, (b) triethylaluminum 27. amylmol, (b) 12 mmol of diisobutylaluminum hydride 1O, (c) 2.3 mmol of diethylaluminium chloride, and +d) 1.85 mmol of acetylacetone, and adding a catalyst prepared by aging at 40° C. for 30 minutes, 1.5 in adiabatic reaction from 70℃
A time reaction was performed. The reaction rate of 1,3-butadiene was almost 100%. To measure Mooney viscosity,
A portion of the polymerization solution was taken out, coagulated, and dried. Mooney viscosity was 49.

Next, after cooling the temperature of the polymerization solution to 60° C., 2.33 ml of (e) diphenyltin dichloride was added. Thereafter, the mixture was stirred for 30 minutes, and the 2,6-di-t-butyl-p
- After adding 3.0 g of cresol, steam coagulation,
It was dried with a hot roll at 100°C. The microstructure of the poly-1,3-butadiene obtained by this reaction has a cis-1,4-bond gold content of 97.3% and a trans-1,4-bond gold content of 1.3%.
3%, and the vinyl bond amount was 1.4%.

Further, Mooney viscosity was 64.

Table 1 shows the results of evaluating the physical properties of the vulcanizate.

Comparative Examples 1 to 2 Comparative Example 1 is a case in which the diphenyltin dichloride of Example 1 is not used, and Comparative Example 2 is a case in which a vulcanizate is prepared using commercially available polybutadiene (manufactured by Japan Synthetic Rubber Co., Ltd., BR-01). This is a comparative example, and the physical property evaluation results of the vulcanizate are shown in Table 1.

From Example 1 and Comparative Examples 1 and 2, it is clear that the polymer of the present invention, in which the active polymer immediately after polymerization with a lanthanum-based rare earth metal catalyst was reacted with diphenyltin chloride, had greatly improved wear resistance. I can see that

Examples 2 to 7 In Example 2, when the amount of diphenyltin dichloride used was increased compared to Example 1, Example 3 and Example 7
is when triphenyltin chloride is used instead of diphenyltin chloride in Example 1, Examples 4 and 5 are when phenyltin trichloride is used in place of diphenyltin chloride in Example 1, and Example 6 is This is an example in which dibutyltin dichloride was used instead of diphenyltin dichloride in Example 1.

Table 1 shows the results of evaluating the physical properties of the vulcanizate.

Comparative Example 3 Poly-1,3-butadiene was produced in the same manner as in Example 1, using carbon tetrachloride instead of diphenyltin dichloride. Table 1 shows the polymerization results and evaluation results of vulcanized physical properties.

Example 8 Poly 1,3-butadiene was produced in the same manner as in Example 1. At this time, the Mooney viscosity before adding component (e) was 43,
The Mooney viscosity after addition was 57, and the microstructure had a cis-1,4 bond content of 97.1% and a trans-1,4 gold content of 97.1%.
- The amount of bonded metal was 1.5%, and the amount of vinyl bonded metal was 1.4%. This poly-1,3-butadiene is designated as Polymer A.

Examples 9 to 11 Example 9 shows the case where triphenyltin chloride was used instead of diphenyltin chloride in Example 8 (polymer B
), Example 10 uses phenyltin trichloride instead of diphenyltin chloride in Example 8 (Polymer C), and Example 11 uses dibutyltin dichloride instead of diphenyltin dichloride in Example 8 (Polymer D). ) is an example. The polymerization results are shown in Table 2.

Comparative Examples 4 to 5 Comparative Example 4 is a case in which the diphenyltin dichloride of Example 8 is not used (Polymer E), and Comparative Example 5 is a case in which carbon tetrachloride is used in place of the diphenyltin dichloride in Example 8 (Polymer F). .

The polymerization results are shown in Table 2.

Test Examples 1 to 4 Polymers A-D obtained in Examples 8 to 11 and natural rubber (NR) were vulcanized according to the above-mentioned formulation, and the evaluation results of the vulcanized physical properties of the vulcanized product were evaluated as follows. It is shown in Table 3.

Comparative Test Examples 1 to 4 Polymer E1 obtained in Comparative Example 4, Polymer F1 obtained in Comparative Example 5, or commercially available polybutadiene (manufactured by Japan Synthetic Rubber ■, BROI), and natural rubber (NR) were combined in the above-mentioned compounding method. Vulcanization was performed according to the recipe, and the evaluation results of the vulcanized physical properties of the vulcanized product are shown in Table 3.

Comparative Test Example 5 10 parts of Polymer A obtained in Example 8 and natural rubber (
Using 90 parts of NR) as a rubber component, vulcanization was performed according to the above formulation, and the evaluation results of the vulcanized physical properties of the vulcanized product were evaluated in the third stage.
Shown in the table.

Test Examples 1 to 4 and Comparative Test Examples 1 to 5 show that the rubber composition containing the conjugated diene polymer of the present invention has excellent wear resistance compared to the conventional rubber composition made of polybutadiene. I know that there is.

〔Effect of the invention〕

The present invention produces a novel conjugated diene polymer by reacting a specific halogenated organometallic with a polymer obtained by polymerizing a conjugated diene using a lanthanum series rare earth metal catalyst in an inert organic solvent. The resulting polymer alone, or a rubber composition obtained by blending it with natural rubber and/or other synthetic rubber, has good exothermic properties and is greatly improved over known conjugated diene polymers. A vulcanizate with excellent abrasion resistance is obtained.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai Procedural amendment (voluntary) IO month 72, 1986

Claims (4)

[Claims] (1) (a) (a) General formula LnY_3 (wherein, Ln is a metal with an atomic number of 57 to 71 in the periodic table, Y is -R,
-OR, -SR, -NR_2, X or RCOO-, where R is a hydrocarbon group having 1 to 20 carbon atoms, and ) General formula AlR^1R^2R^3 (where R^1, R^2 and R^3 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and if all are hydrogen atoms ), obtained by polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst containing (c) a Lewis acid and/or (d) a Lewis base as required. (b) general formula R'_nMX_4_-_n (in the formula, R'
is an alkyl group or aryl group having 1 to 20 carbon atoms, M is a tin atom or germanium atom, X is a halogen atom, and n is an integer of 1 to 3). A method for producing a conjugated diene polymer characterized by: (2) The method for producing a conjugated diene polymer according to claim 1, wherein the conjugated diene is 1,3-butadiene. (3) The method for producing a conjugated diene polymer according to claim 1 or 2, wherein M in the halogenated organometallic is tin. (4) Mooney viscosity of conjugated diene polymer is 10 to 12
0. The method for producing a conjugated diene polymer according to claim 1, 2, or 3, wherein the conjugated diene polymer is 0.