JPH1135633A - Production of conjugated diene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having narrow molecular weight distribution and capable of exhibiting excellent mechanical characteristics, processability and abrasion resistance by polymerizing a conjugated diene-based compound by using a catalyst system in which specific components are combined. SOLUTION: (A) A conjugated diene-based compound is polymerized by using (B) a catalyst consisting essentially of (i) a rare earth element-containing compound having 57-71 atomic number of the periodic table or a reaction compound of these compounds with a Lewis base, (ii) alumoxane, (iii) an organoaluminum compound of the formula AlR<1> R<2> R<3> (R<1> to R<2> are each a 1-10C hydrocarbon group or H; R<3> is a 1-10C hydrocarbon group) and (iv) a silicon halide compound and/or a halogenated organosilicon compound to provide the objective conjugated diene-based polymer. The active terminal of the resultant polymer is successively reacted (or modified) with a specific compound to form the objective polymer in which molecular weight of the polymer is increased or polymer chain is branched.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel conjugated diene polymer.

[0002]

2. Description of the Related Art Conjugated diene polymers play an extremely important role in industry, and many proposals have been made for polymerization catalysts for conjugated diene compounds.
It plays an extremely important role in industry. In particular, thermal
In order to obtain a conjugated diene polymer having improved mechanical properties, a number of polymerization catalysts giving a high cis-1,4-bond content have been studied and developed. For example,
Composite catalyst systems containing transition metal compounds such as nickel, cobalt and titanium as main components are known, and some of them are already widely used industrially as polymerization catalysts for butadiene, isoprene and the like [End. Ing. Che
m. , 48, 784 (1956), Japanese Patent Publication No. 37-819.
No. 8].

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 to III organic metal compound has been studied and developed. Research on stereospecific polymerization has been actively conducted [Makromol. Chem. Su
ppl. , 4, 61 (1981); Polym. S
ci, Polym. Chem. Ed. , 18,3345
(1980), German Patent Application No. 2,848,964, Sci, Sinica. , 2/3, 734 (1
980), Rubber. Chem. Techno
l. , 58, 117 (1985)].

Japanese Patent Publication No. 47-14729 discloses 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 halide such as trialkyl aluminum and ethyl aluminum dichloride. In particular, it has been shown that aging the catalyst in the presence of butadiene increases the catalytic activity. Furthermore, Japanese Patent Publication No. 62-14
No. 04, JP-B-63-64444, JP-B-1
Japanese Patent Application No. 16244 proposes a method for increasing the catalytic activity by increasing the solubility of a compound in a polymerization solvent for a rare earth element. Furthermore, Japanese Patent Publication No. Hei 4-2601 discloses that a catalyst system comprising a rare earth metal compound, a trialkylaluminum or aluminum halide and an organic halogen derivative has a higher activity in the polymerization of 1,3-butadiene than before. ing. However, a polymer obtained by a conventional catalyst system containing a rare earth metal compound has a wide molecular weight distribution and does not sufficiently improve wear resistance and resilience.

[0005] JP-A-6-212916, JP-A-6-219916
JP-A-306113 and JP-A-8-73515 show that when a catalyst system using methylalumoxane as a neodymium compound is used, a conjugated diene polymer having high polymerization activity and a narrow molecular weight distribution can be obtained. It has been reported. However, in the above polymerization method, in order to maintain sufficient catalytic activity and obtain a polymer having a narrow molecular weight distribution, a large amount of alumoxane is required in comparison with a neodymium compound in comparison with a conventional catalyst system using an organoaluminum compound. And the price is higher than ordinary organoaluminum compounds, and the cold flow is large and there is a problem in storage stability and the like, which is practically problematic.

[0006]

The inventors of the present invention have made intensive studies and have found that a rare earth metal compound, an alumoxane, an organoaluminum compound, and a catalyst system comprising a combination of a silicon halide compound and / or a halogenated organosilicon compound. When using alumoxane, the catalytic activity is sufficiently high even if the amount of alumoxane used is small, and a conjugated diene polymer having a narrow molecular weight distribution can be obtained, and the obtained polymer has excellent mechanical properties, workability, and abrasion resistance. Have reached the present invention.

[0007]

According to the present invention, there is provided a process for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using a catalyst containing the following components (a) to (d) as main components. It provides a method. (A) component: a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a compound obtained by reacting these compounds with a Lewis base (hereinafter also referred to as “rare earth metal compound”) (b) component: alumoxane (C) component; AlR ¹ R ² R ³ (wherein, R ^{1 to} R ² are the same or different and are a hydrocarbon group containing 1 to 10 carbon atoms or a hydrogen atom, and R ³ is 1 to 10 carbon atoms) Wherein R ³ is the above-mentioned R ¹ or R ¹
Organoaluminum compounds corresponding to ² may be the same or different from) (d) component; halogenated silicon compound and / or a halogenated organic silicon compound (also hereinafter referred to as "silicon compound"), the present invention, the polymerization After the reaction, a method for producing a conjugated diene polymer characterized by reacting at least one compound selected from the group consisting of the following components (e) to (j) (hereinafter also referred to as “modification”): To provide. (E) component: R ⁴ _n M′X _4-n , M′X ₄ , M′X ₃ ,
R ⁴ _n M '(-R ⁵ -COOR ⁶ ) _4-n or R
⁴ _n M '(-R ⁵ -COR ⁶ ) _4-n (wherein, R ^{4 to} R ⁵
Are the same or different and are each a hydrocarbon group containing 1 to 20 carbon atoms, R ⁶ is a hydrocarbon group containing 1 to 20 carbon atoms, and contains a carbonyl group or an ester group in the side chain. M ′ is a tin atom, silicon atom, germanium atom or phosphorus atom, X is a halogen atom, n
Is an integer of 0 to 3), a halogenated organometallic compound, a metal halide compound or an organometallic compound (f) component; in the molecule, a Y = C = Z bond (where Y is a carbon atom, A heterocumulene compound containing an oxygen atom, a nitrogen atom or a sulfur atom, and Z is an oxygen atom, a nitrogen atom or a sulfur atom) (g) component;

[0008]

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[0009] (wherein, Y 'represents an oxygen atom, a nitrogen atom or a sulfur atom) bonded hetero three-membered ring compound containing a component (h); halogenated isocyano compound of component (i); R ⁷ - ( COOH) _m , R ⁸ (CO
^{_{X) m, R 9 - (}} COO-R 10), R 11 -OCOO-R
^{12, R 13 - (COOCO-} R 14) m or,

[0010]

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

[0012]

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Wherein R ^{16 to} R ²² are the same or different,
A hydrocarbon group containing 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom;
A metal salt of a carboxylic acid corresponding to

[0014]

DETAILED DESCRIPTION OF THE INVENTION (a) Used in the catalyst of the present invention
The component is a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table or a compound obtained by reacting these compounds with a Lewis base. Preferred elements are neodymium, praseodymium, cerium, lanthanum,
It is gadolinium or 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 primary, secondary or tertiary. Attached to a carbon atom. Specifically, octanoic acid, 2-ethyl-hexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, and versatic acid (trade names manufactured by Shell Chemical Co., Ltd., in which the carboxyl group is a tertiary carbon atom) Is a carboxylic acid bonded to the compound of formula (1), and salts of 2-ethyl-hexanoic acid, naphthenic acid and versatic acid are preferred.

The alkoxide of the rare earth element is represented by the general formula (R ²⁴ O) ₃ M (M is an atomic number of 57 to 71 in the periodic table.
And R ²⁴ has 1 to 1 carbon atoms.
20 hydrocarbon groups, preferably a saturated or unsaturated alkyl group, and a long-chain, branched or cyclic alkyl group, and the carboxyl group is bonded to a primary, secondary or tertiary carbon atom. I have. Examples of the alkoxy group represented by R ²⁴ O, 2-ethyl - hexyl alkoxy group, oleyl alkoxy group, stearyl alkoxy group, phenoxy group, and benzyl alkoxy group. Of these, preferred are a 2-ethyl-hexylalkoxy group and a benzylalkoxy group.

The β-diketone complex of a rare earth element includes
Rare earth element acetylacetone, benzoylacetone, propionylacetone, valerylacetone, ethylacetylacetone complex and the like can be mentioned. Among them, preferred are acetylacetone complex and ethylacetylacetone complex.

The rare earth element phosphates or phosphites include rare earth elements such as bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, bis (p-nonylphenyl) phosphate, and the like. Bis (polyethylene glycol-p-nonylphenyl) phosphate, (1-methylheptyl) phosphate (2-ethylhexyl), (2-ethylhexyl) phosphate (p-nonylphenyl), mono-2-ethyl 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-ethyl-hexanoate and neodymium versatate.

The Lewis base used for easily solubilizing the rare earth element-containing compound in a solvent is 0 to 30 mol, preferably 1 to 10 mol, per 1 mol of the rare earth metal compound. Or a product obtained by reacting both in advance. Here, examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorus compounds, and monohydric or dihydric alcohols. The above component (a) can be used alone or in combination of two or more.

The alumoxane (b) used in the catalyst of the present invention is a compound having a structure represented by the formula (I) or (II). Also, Fine Chemical, 23,
(9), 5 (1994); Am. Chem. So
c. , 115, 4971 (1993); Am. Ch
em. Soc. , 117, 6465 (1995).

[0021]

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(Wherein, R ²⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 2 or more.) In the alumoxane represented by the formula (I) or (II), Examples of the hydrocarbon group represented by R ²⁵ 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.

(B) The alumoxane may be produced by any known technique, for example, benzene, toluene,
In an organic solvent such as xylene, add trialkylaluminum or dialkylaluminum monochloride,
Further, it can be produced by adding water, water vapor, water vapor-containing nitrogen gas or a salt having water of crystallization such as copper sulfate pentahydrate or aluminum sulfate hexahydrate to react. The above (b) alumoxane can be used alone or in combination of two or more.

(C) AlR ¹ used in the catalyst of the present invention
R ² R ³ (wherein, R ^{1 to} R ² are the same or different and are a hydrocarbon group or a hydrogen atom containing 1 to 10 carbon atoms, and R ³ is a hydrocarbon containing 1 to 10 carbon atoms) Wherein R ³ may be the same as or different from R ¹ or R ² ), for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
Triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, di-n-propyl hydride Aluminum, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, dioctyl aluminum hydride, diisooctyl aluminum hydride, ethyl aluminum dihalide, n-propyl aluminum di Halide, isobutylaluminum dihalide and the like, preferably triethylaluminum, triisobutylaluminum, hydrogen Diethylaluminum, hydrogenated diisobutylaluminum. The organoaluminum compound (c) of the present invention can be used alone or in combination of two or more.

The component (d) used in the catalyst of the present invention is a silicon halide compound and / or a halogenated organosilicon compound. Among the component (d), examples of the silicon halide compound include silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, and hexachlorodisilane. In the component (d), 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 , Vinylmethyldichlorosilane, vinyldimethylchlorosilane, chloromethylsilane, chloromethyltrimethylsilane, chloromethyldimethylchlorosilane, chloromethylmethyldichlorosilane, chloromethyltrichlorosilane, dichloromethylsilane, dichloromethylmethyldichlorosilane, dichloromethyldimethylchlorosilane, Dichlorotetramethyldisilane, tetrachlorodimethylsilane, bisque B dimethylsilyl ethane, dichloro tetramethyldisiloxane, trimethylsiloxy dichlorosilane, trimethylsiloxy dimethyl chlorosilane, and tris trimethylsiloxy dichlorosilane and the like. As the component (d), preferably, silicon tetrachloride, triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, ethyltrichlorosilane,
Methyltrichlorosilane, trichlorosilane, dichlorotetramethyldisilane, dichlorotetramethyldisiloxane, and more preferably silicon tetrachloride. The above component (d) can be used alone or
Mixtures of more than one species can be used.

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
0.0001 to 1. 0 g of the conjugated diene compound.
It is preferable to use an amount of 0 mmol. If the amount is less than 0.0001 mmol, the polymerization activity becomes low, which is not preferable.
If it exceeds 1.0 mmol, the catalyst concentration becomes high, and a deashing step is required, which is not preferable. In particular, 0.0005-
It is preferred to use an amount of 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), and the ratio of the component (a) to the component (b) is 1: 1 to 1 in terms of molar ratio. : 500, preferably 1:
3 to 1: 250, more preferably 1: 5 to 1: 100
It is. Further, the amount of the component (c) used is determined by the component (a):
The component (c) is in a molar ratio of 1: 1 to 1: 300, preferably 1: 3 to 1: 150. Further, the amount of the component (d) used is such that the molar ratio of the component (a) and the component (d) is 1: 1:
0.1 to 1:30, preferably 1: 0.2 to 1:15. If the amount of the catalyst or the catalyst 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 (d), 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), the component (c) and the component (d), if necessary, a conjugated diene-based compound and / or a non-conjugated diene-based compound may be added in an amount of 0 per mole of the compound (a).
It may be used in a proportion of up to 50 mol. As the conjugated diene-based compound used for the production of the catalyst, 1,3-butadiene, isoprene and the like can be used as in the case of the monomer for polymerization. Examples of the non-conjugated diene compound include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene. A conjugated diene-based compound and / or a non-conjugated diene-based compound as a catalyst component is not essential, but when used together, there is an advantage that the catalytic activity is further improved.

The catalyst is produced by, for example, reacting the components (a) to (d) 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 period of the polymerization initiation derivative. Here, the aging temperature is 0 to 100 ° C, preferably 20 to 80 ° C. 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 unpreferably increased. 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 (d) 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, etc., and particularly preferably 1,3-
Butadiene, isoprene and 1,3-pentadiene. These conjugated diene-based compounds can be used alone or in combination of two or more. When two or more are used in combination, a copolymer is obtained.

The conjugated diene polymer of the present invention can be used with or without a solvent. The polymerization solvent is an inert organic solvent, for example, a saturated aliphatic hydrocarbon having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane; and a saturated alicyclic having 6 to 20 carbon atoms such as cyclopentane and cyclohexane. Formula hydrocarbon, 1-butene,
Monoolefins such as 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorobenzene And halogenated hydrocarbons such as toluene.

The polymerization temperature is usually -30 ° C to +200
° C, preferably from 0 to + 150 ° C. The polymerization reaction may be a batch type or a continuous type. When a polymerization solvent is used, the concentration of the monomer in the solvent is usually 5 to 50% by weight, preferably 7 to 35% by weight. 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 before modification obtained using the catalyst containing the components (a) to (d) as a main component is cis-
The 1,4-bond content is preferably 90% or more, more preferably 92% or more, and the 1,2-vinyl bond content is preferably 2.5% or less, more preferably 2.0% or less. Outside these ranges, the mechanical properties and wear resistance will be poor. The cis 1,4- of these conjugated diene polymers
Adjustment of the microstructure such as the bond content can be easily performed by controlling the catalyst composition ratio and the polymerization temperature.

In the present invention, Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the obtained conjugated diene polymer, is preferably 3.5.
Or less, more preferably 3.3 or less. If it exceeds 3.5, the wear resistance is poor. The adjustment of Mw / Mn can be easily performed by controlling the molar ratio of the above components (a) to (d). Furthermore, the Mooney viscosity of the above conjugated diene polymer (ML _{1 + 4} , 100 ° C.)
Is preferably 10 to 100, more preferably 15 to
90 range. If it is less than 10, the mechanical properties and abrasion resistance after vulcanization are inferior. On the other hand, if it exceeds 100, the workability during kneading is inferior and the mechanical properties are deteriorated. Further, the molecular weight of the conjugated diene-based polymer obtained in the present invention can be changed over a wide range, the weight average molecular weight in terms of polystyrene is usually 50,000 to 1.5 million,
Preferably, it is 100,000 to 1,000,000, and if it is less than 50,000, it becomes a liquid polymer, while if it exceeds 1.5 million, processability is poor, and torque is excessively applied at the time of kneading with a roll or a banbury, or the compounded rubber is heated to a high temperature. This leads to problems such as poor carbon black dispersion and poor performance of the vulcanized rubber.

The desired conjugated diene-based polymer is recovered by adding a polymerization terminator and a polymer stabilizer to the reaction system, if necessary, and by a known solvent removal and drying operation in the production of the conjugated diene-based polymer. I can do it.

In the present invention, the conjugated diene compound is polymerized by using the rare earth element compound catalyst as described above, and then a specific compound is reacted (modified) with the active terminal of the obtained polymer to obtain a polymer. It is possible to form a new polymer in which the molecular weight of the coalescence is increased or the polymer chain is branched. This modification improves wear resistance, mechanical properties and cold flow.

In the present invention, (e) a halogenated organometallic compound or a metal halide compound to be reacted with the active terminal of the polymer is represented by the following formula (III). (Wherein, R ⁴ is a hydrocarbon group containing 1 to 20 carbon atoms, M ′ is a tin atom, a silicon atom, a germanium atom or a phosphorus atom, X is a halogen atom, and n is an integer of 0 to 3. In the above formula (III), when M ′ is a tin atom, as the component (e), for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin 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, as the component (e), for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldisilane Examples thereof include chlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenylchlorosilane, hexyltridichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, and silicon tetrachloride.

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

In the present invention, as the component (e), an organometallic compound containing an ester group represented by the following formula (IV) or a carbonyl group represented by the following formula (V) in the molecule is used. You can also. _{^{R 4 n M '(- R}} 5 -COOR 6) 4-n ··· (IV) R 4 n M' (- R 5 -COR 6) in _4-n ··· (V) (wherein, R ⁴ To R ⁵ are the same or different and have 1 to 2 carbon atoms.
A hydrocarbon group containing 0 carbon atoms, and R ⁶ has 1 to 20 carbon atoms.
And a hydrocarbon group containing a carbonyl group or an ester group in the side chain, and M ′ is a tin atom, a silicon atom, a germanium atom or a phosphorus atom, X
Is a halogen atom, and n is an integer of 0 to 3. ) These components (e) may be used in combination at any ratio.

The heterocumulene compound (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 bond (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.) In 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. Y is a nitrogen atom, and Z is an oxygen atom. In the case of is a isocyanate compound, when Y is a nitrogen atom, when Z is a sulfur atom, it is a thioisocyanate compound, when both Y and Z are a nitrogen atom, it is a carbodiimide compound, Y and Z are both In the case of an oxygen atom, it is carbon dioxide, when Y is an oxygen atom, and when Z is a sulfur atom, it is carbonyl sulfide;
When both and Z are sulfur atoms, they are carbon disulfide. However, the component (f) is not limited to these combinations.

Among these, 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,
Examples thereof include 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, and hexamethylene diisocyanate. Examples of the thioisocyanate compound include phenylthioisocyanate, 2,4-tolylenedithioisocyanate, hexamethylenedithioisocyanate and the like. Examples of the carbodiimide compound include N, N'-diphenylcarbodiimide,
N, N'-ethylcarbodiimide and the like can be mentioned.

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

[0043]

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(In the formula, Y ′ is an oxygen atom, a nitrogen atom or a sulfur atom.) Here, among the components (g), when Y ′ is an oxygen atom, it is an epoxy compound, In the case of an elemental atom, 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 is exemplified. Examples of the ethyleneimine derivative include ethyleneimine, propyleneimine, N-phenylethyleneimine, and N- (β-
(Cyanoethyl) ethyleneimine and the like. Furthermore, examples of the thiirane compound include thiirane, methylthiirane, and phenylthiirane.

The halogenated isocyano compound (h) to be reacted with the active terminal of the polymer is a compound having a structure represented by the following formula (VIII). (In the formula, X is a halogen atom.) (H) As the halogenated isocyano compound, 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 (i) carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride to be reacted with the active terminal of the polymer is represented by the following formulas (VIV) to (XV).
It is a compound having a structure represented by IV). _{^{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)

[0047]

Embedded image

(Wherein R ^{7 to} R ¹⁵ are the same or different,
A hydrocarbon group containing 1 to 50 carbon atoms, X is a halogen atom, and m is an integer of 1 to 5. 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. And terephthalic acid, trimellitic acid, pyromellitic acid, melitic acid, polymethacrylic acid ester compounds or all or partial hydrolysates of polyacrylic acid compounds.

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 phthalic acid chloride. Acid chloride, maleic acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, benzoyl fluoride and the like can be mentioned.

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 include formula (XI) such as acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptanoic anhydride, benzoic anhydride, and cinnamic anhydride.
Intermolecular acid anhydrides represented by II), succinic anhydride,
Examples include intramolecular acid anhydrides represented by the formula (XIV) such as methyl succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, phthalic anhydride, and styrene-maleic anhydride copolymer.

The compounds listed as the component (i) contain an aprotic polar group such as an ether group or a tertiary amino group in the coupling agent molecule within a range not to impair the object of the present invention. It may be something. 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. Also,
The component (i) may be a single compound or a mixture of two or more of these compounds. Further, a compound containing a free alcohol group or a phenol group may be contained as an impurity.

The metal salt of carboxylic acid (j) to be reacted with the active terminal of the polymer has a structure represented by the following formulas (XV) to (XVII).

[0053]

Embedded image

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

Here, among the components (j), the above equation (X
Examples of the compound represented by V) include triphenyltin laurate, triphenyltin-2-ethylhexate, triphenyltin naphthate, triphenyltin acetate, triphenyltin acrylate, and tri-n
-Butyltin laurate, tri-n-butyltin-2-
Ethyl hexatate, 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
-Ethyl hexatate, triisobutyltin naphthate, triisobutyltin acetate, triisobutyltin acrylate, triisopropyltin laurate, triisopropyltin-2-ethylhexate, triisopropyltin naphthate, triisopropyltin acetate, triisopropyl Tin acrylate, trihexyltin laurate, trihexyltin-2-ethylhexate, trihexyltin acetate, trihexyltin acrylate, trioctyltin laurate, trioctyltin-2-ethylhexate, trioctyltin naphthalate , Trioctyltin acetate, trioctyltin acrylate, tri-2-ethylhexyltin laurate, tri-2-ethylhexyltin-2-
Ethyl hexatate, tri-2-ethylhexyltin naphthate, tri-2-ethylhexyltin acetate,
Tri-2-ethylhexyltin acrylate, tristearyltin laurate, tristearyltin-2-ethylhexate, tristearyltin naphate, tristearyltin acetate, tristearyltin acrylate, tribenzyltin laurate, tribenzyltin- 2-ethylhexate, tribenzyltin naphthate, tribenzyltin acetate, tribenzyltin acrylate, diphenyltin dilaurate, diphenyltin-2-ethylhexate, diphenyltin distearate, diphenyltin dinaphate, diphenyltin diacetate, diphenyltin diacrylate , Di-n-butyltin dilaurate, di-n-butyltin di-2-ethylhexate, di-n-butyltin distearate, di-n Butyl tin di-naphthoquinone Tate, 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 dinaphthate, -T-butyltin diacetate, di-t-butyltin diacrylate, diisobutyltin dilaurate,
Diisobutyltin di-2-ethylhexate, diisobutyltin distearate, diisobutyltin dinaphate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate,
Diisopropyltin-2-ethylhexate, diisopropyltin distearate, diisopropyltin dinaphthate, diisopropyltin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexate, dihexyltin distearate Dihexyltin dinaphthate, dihexyltin diacetate, dihexyltin diacrylate, di-2-ethylhexyltin dilaurate, di-2-ethylhexyltin-2-ethylhexate, di-2-ethylhexyltin distearate, di- 2-ethylhexyltin dinaphthate, di-2-ethylhexyltin diacetate, di-2-ethylhexyltin diacrylate, dioctyltin dilaurate, dioctyltin di-2 Ethyl hexatate, dioctyltin distearate, dioctyltin dinaphthate, dioctyltin diacetate, dioctyltin diacrylate, distearyltin dilaurate, distearyltin di-2-ethylhexate, distearyltin distearate, distearyl Stearyl tin dinaphthate, distearyl tin diacetate, distearyl tin diacrylate, dibenzyl tin dilaurate, dibenzyl tin di-
2-ethylhexate, dibenzyltin distearate, dibenzyltin dinaphate, dibenzyltin diacetate, dibenzyltin diacrylate, phenyltin trilaurate, phenyltin tri-2-ethylhexate, phenyltin Trinaphthate, phenyltin triacetate, phenyltin triacrylate, n-
Butyltin trilaurate, n-butyltin tri-2-
Ethyl hexatate, n-butyltin trinaphthate,
n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2-ethylhexate, t-butyltin trinaphthate, t-butyltin triacetate, t-
Butyltin triacrylate, isobutyltin trilaurate, isobutyltin tri-2-ethylhexate, isobutyltin trinaphate, isobutyltin triacetate, isobutyltin triacrylate, isopropyltin trilaurate, isopropyltin tri-
2-ethyl hexatate, isopropyltin trinaphate, isopropyltin triacetate, isopropyltin triacrylate, hexyltin trilaurate,
Hexyltin tri-2-ethyl hexatate, hexyl tin trinaphate, hexyl tin triacetate, hexyl tin triacrylate, octyl tin trilaurate, octyl tin tri-2-ethyl hexatate, octyl tin trinaphate, octyl tin triacetate Octyltin triacrylate, 2-ethylhexyltin trilaurate, 2-ethylhexyltin trilaurate
2-ethylhexate, 2-ethylhexyltin trinaphate, 2-ethylhexyltin triacetate,
2-ethylhexyltin triacrylate, stearyltin trilaurate, stearyltin tri-2-ethylhexate, stearyltin trinaphate, stearyltin triacetate, stearyltin triacrylate, benzyltin trilaurate, benzyltin tri-2- Ethyl hexatate, benzyltin trinaphate, benzyltin triacetate, benzyltin triacrylate and the like can be mentioned.

Examples of the compound represented by the above formula (XVI) include diphenyltin bismethylmalate,
Diphenyl tin bis-2-ethyl hexatate, diphenyl tin bis octyl malate, diphenyl tin bis octyl malate, diphenyl tin bis benzyl malate, di-n-butyl tin bis methyl malate, di-n-
Butyltin bis-2-ethylhexate, di-n-butyltin bisoctylmalate, di-n-butyltinbisbenzylmalate, di-t-butyltinbismethylmalate, di-t-butyltinbis-2-ethylhexa Tate, di-t-butyltin bisoctyl malate, di-
t-butyltin bisbenzylmalate, diisobutyltinbismethylmalate, diisobutyltinbis-2-ethylhexate, diisobutyltinbisoctylmalate, diisobutyltinbisbenzylmalate, diisopropyltinbismethylmalate, diisopropyltinbis- 2-ethyl hexatate, diisopropyl tin bis octyl malate, diisopropyl tin bis benzyl malate, dihexyl tin bis methyl malate, dihexyl tin bis-2-ethyl hexatate, dihexyl tin bis octyl malate, dihexyl tin bis benzyl malate , Di-2-ethylhexyltin bismethylmalate, di-2-ethylhexyltin bis-2-ethylhexate, di-2-ethylhexyltin bisoctylmalate, di-2 Ethylhexyltin bisbenzyl malate, dioctyltin bismethylmalate, dioctyltin bis-2-ethylhexate, dioctyltin bisoctylmalate, dioctyltin bisbenzylmalate, distearyltin bismethylmalate, distearyltin bis -2-ethyl hexatate, distearyl tin bisoctyl malate, distearyl tin bisbenzyl malate, dibenzyl tin bismethyl malate,
Dibenzyl tin bis-2-ethyl hexatate, dibenzyl tin bis octyl malate, dibenzyl tin bis benzyl malate, diphenyl tin bis methyl acetate, diphenyl tin bis-2-ethyl hexatate, diphenyl tin bis octyl acetate, diphenyl tin bis benzyl acetate , Di-n-butyltin bismethyl acetate, di-n-butyltin bis-2-ethylhexate, di-n-butyltin bisoctyl acetate, di-n-butyltin bisbenzyl acetate, di-
t-butyltin bismethyl acetate, di-t-butyltin bis-2-ethylhexate, di-t-butyltin bisoctyl acetate, di-t-butyltin bisbenzyl acetate, diisobutyl tin bismethyl acetate, diisobutyl tin bis-2- Ethyl hexatate, diisobutyltin bisoctyl acetate, diisobutyltin bisbenzyl agitate, diisopropyltin bismethyl acetate, diisopropyltin bis-2
-Ethyl hexatate, diisopropyltin bisoctyl acetate, diisopropyltin bisbenzyl acetate, dihexyltin bismethyl acetate, dihexyl tin bis-2-ethyl hexatate, dihexyl tin bismethyl acetate, dihexyl tin bisbenzyl acetate, di-2-ethyl hexyl Tin bismethyl acetate, di-2-ethylhexyltin bis-2-ethylhexate, di-2-ethylhexyltin bisoctyl acetate, di-2-ethylhexyl tin bisbenzyl acetate, dioctyl tin bismethyl acetate,
Dioctyltin bis-2-ethylhexate, dioctyltin bisoctyl agitate, dioctyltin bisbenzyl acetate, distearyl tin bismethyl acetate, distearyl tin bis-2-ethyl hexatate, distearyl tin bisoctyl acetate, distearyl tin Bisbenzyl acetate, dibenzyl tin bismethyl acetate, dibenzyl tin bis-2-ethyl hexatate, dibenzyl tin bis octyl agitate, dibenzyl tin bis benzyl acetate and the like can be mentioned.

Further, as the compound represented by the above formula (XVII), for example, diphenyltin malate, di-n
-Butyltin malate, di-t-butyltinmalate,
Diisobutyl tin malate, diisopropyl tin malate, dihexyl tin malate, di-2-ethylhexyl tin malate, dioctyl tin malate, distearyl tin malate, dibenzyl tin malate, diphenyl tin agitate, di-n-butyl tin agitate , Di-t
-Butyltin agitate, diisobutyltin agitate, diisopropyltin agitate, dihexyltin diacetate, di-2-ethylhexyltin agitate,
Dioctyltin agitate, distearyltin agitate, dibenzyltin agitate and the like. The compounds of the above components (e) to (j) (hereinafter also referred to as "modifiers") can be used alone or in combination of two or more.

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 terms of molar ratio. However, the effect of improving wear resistance and cold flow is not exhibited.
The effect of improving the physical properties is saturated, and it is not preferable from the viewpoint of economy and, in some cases, a toluene-insoluble matter (gel). This denaturation reaction is performed at + 160 ° C. or lower, preferably -30 ° C.
It is desirable to carry out the reaction at a temperature of + 130 ° C. with stirring for 0.1 to 10 hours, preferably 0.2 to 5 hours.

After the modification reaction is completed, the catalyst is inactivated, and if necessary, a polymer stabilizer is added to the reaction system to remove the solvent. And can be recovered by a drying operation.

The conjugated diene-based polymer obtained according to the present invention is blended with this polymer alone or with another synthetic rubber or natural rubber, and if necessary, oil-extended with a process oil. Next, fillers such as carbon black, vulcanizing agents, vulcanization accelerators, and other usual compounding agents are added and vulcanized, and treads and side tires for winter tires such as passenger cars, trucks, bus tires, and studless tires are added. Used for rubber applications requiring mechanical properties, workability, and abrasion resistance, such as walls, various members, hoses, belts, vibration-proof rubbers, 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 for use.

[0061]

EXAMPLES Hereinafter, the present invention will be described more specifically 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. Microstructure (cis-1,4-bond content, vinyl-1,2
-Bonding content ) It was determined by an infrared method (Morello method). Ratio between weight average molecular weight (Mw) and number average molecular weight (Mn)
(Mw / Mn) Measurement was performed under the following conditions using a HLC-8120GPC manufactured by Tosoh Corporation and a differential refractometer as a detector. Column: Tosoh Corporation, column GMHHXL Mobile phase: Tetrahydrofuran

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%.

The polymer of the present invention was kneaded and compounded using a plastmill according to the following compounding recipe. Press vulcanization was performed at 145 ° C. for an optimum time. Compounding formulation (part) Polymer 50 Natural rubber 50 ISAF 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

Example 1 A nitrogen-substituted autoclave having an internal volume of 5 liters
Under nitrogen, 2.4 kg of cyclohexane and 300 g of 1,3-butadiene were charged. To these are added in advance a cyclohexane solution of neodymium octoate (0.09 mmol), a toluene solution of methylalumoxane (2.7 mmol), diisobutylaluminum hydride (4.7 mmo).
l) and a solution of silicon tetrachloride in cyclohexane (0.0
9 mmol) with 1,3-butadiene in an amount 5 times the amount of neodymium was reacted and aged at 50 ° C. for 30 minutes.
Polymerization was carried out at 30 ° C for 30 minutes.

After completion of the polymerization, 2,4-di-t-butyl-p
Adding a methanol solution containing 0.3 g of cresol;
After termination of the polymerization, the solvent was removed by steam stripping,
The polymer was dried with a roll at 110 ° C. to obtain a polymer. The yield of this polymer was 290 g and the Mooney viscosity (ML _{1 + 4} , 100
C) is 44, the cis-1,4-bond content is 97.0%,
The 1,2-vinyl bond content is 1.2%, and Mw / Mn is 2.
It was one.

Example 2 In Example 1, the amount of methylalumoxane added was 4.5 mm.
A polymer was obtained in the same manner as in Example 1 except that ol was used. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 3 In Example 1, the amount of methylalumoxane added was 9.0 mm.
A polymer was obtained in the same manner as in Example 1 except that ol was used. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 4 In Example 1, the amount of silicon tetrachloride added was 0.18 mmol.
A polymer was obtained in the same manner as in Example 1 except that the polymer was replaced with Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 5 In Example 1, the amount of silicon tetrachloride was changed to 0.45 mmol.
A polymer was obtained in the same manner as in Example 1 except that the polymer was replaced with Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 6 A polymer was obtained in the same manner as in Example 1 except that neodymium octeneate was replaced by neodymium versatate. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 7 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was replaced with trimethylchlorosilane.
Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 8 A polymer was obtained in the same manner as in Example 1, except that dimethyldichlorosilane was used instead of silicon tetrachloride.
Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 9 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was changed to methyldichlorosilane. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 10 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was replaced with diethyldichlorosilane.
Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 11 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was replaced with methyltrichlorosilane.
Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 12 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was changed to ethyltrichlorosilane.
Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 13 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was replaced with trichlorosilane. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 14 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was changed to dichlorotetramethyldisilane. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 15 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was changed to dichlorotetramethyldisiloxane. Table 1 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was not used. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the physical properties of the vulcanized product.
Shown in

Comparative Example 2 A polymer was obtained in the same manner as in Example 1 except that methylalumoxane was not used. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Comparative Example 3 A polymer was obtained in the same manner as in Example 1 except that diisobutylaluminum hydride was not used. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Comparative Example 4 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was changed to diethylaluminum chloride. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Comparative Example 5 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was changed to t-butyl chloride. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Comparative Example 6 The vulcanization properties of a commercially available polybutadiene rubber [Polybutadiene rubber BR01 manufactured by Nippon Synthetic Rubber Co., Ltd.] are shown in Table 2.

Example 16 A nitrogen-substituted autoclave having an internal volume of 5 liters was prepared.
Under nitrogen, 2.5 kg of cyclohexane and 300 g of 1,3-butadiene were charged. To these, a cyclohexane solution containing neodymium octoate (0.09 mmol) in advance, a toluene solution of methylalumoxane (2.7 mmol), and diisobutylaluminum hydride (5.2
mmol) in hexane and silicon tetrachloride (0.0
9 mmol) of a cyclohexane solution, and a catalyst which had been reacted and aged at 25 ° C. for 30 minutes with 1,3-butadiene in an amount 5 times the amount of neodymium was charged, and polymerization was carried out at 50 ° C. for 30 minutes.

Next, the temperature of the polymerization solution was maintained at 50 ° C., and a solution of butyltin trichloride (3.6 mmol) in cyclohexane was added.
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. Mooney viscosity of this polymer (ML
_{1 + 4} , 100 ° C.) is 45, and the cis-1,4-bond content is 9
6.9%, 1,2-vinyl bond content is 1.2%, Mw /
Mn was 2.4. Table 2 shows the evaluation results of the physical properties of the vulcanized product.

Example 17 Example 1 was repeated, except that the modifying agent was replaced by polymeric type diphenylmenthane diisocyanate.
A polymer was obtained in the same manner as in 6. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 18 A polymer was obtained in the same manner as in Example 16 except that the modifying agent was changed to diethyl adipate. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 19 A polymer was obtained in the same manner as in Example 16 except that the modifier was changed to styrene oxide. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 20 In Example 16, the modifying agent was 2,4,6-trichloro-1,
A polymer was obtained in the same manner as in Example 16 except that 3,5-triazine was used. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

Example 21 A polymer was obtained in the same manner as in Example 16, except that the modifying agent was changed to dioctyltinbisoctylmalate. Table 2 shows the results of analyzing the properties of the obtained polymer and the results of evaluating the properties of the vulcanized product.

In Examples 1 to 6, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) was smaller than that of Comparative Examples 1 to 3, and the breaking strength after vulcanization and the repulsion It can be seen that the elasticity and wear resistance are improved, and the components (a), (b), (c) and (d) are essential. Further, from Comparative Examples 4 and 5, even when the amount of methylalumoxane used was the same, the present catalyst system had smaller Mw / Mn, had better physical properties after vulcanization, and reduced the amount of methylalumoxane used. You can see what you can do. Further, from Examples 7 to 15, it can be seen that there is no problem in the catalytic activity, the polymer structure and the physical properties after vulcanization even with the halogenated organosilicon compound. Further, from Examples 16 to 21, it can be seen that by modifying the active terminal of the polymer with a modifier after the polymerization, the rebound resilience and abrasion resistance are improved as compared with the unmodified polymer.

[0095]

[Table 1]

[0096]

[Table 2]

* 1) Ratio between weight average molecular weight (Mw) and number average molecular weight (Mn) * 2) Comparative Example 6 was set to 100, and the larger the numerical value, the better. * 3) Commercially available polybutadiene rubber [Nippon Synthetic Rubber Co., Ltd. )
* 4) Polymeric type diphenylmethane diisocyanate * 5) Styrene oxide * 6) 2,4,6-Trichloro-1,3,5-triazine * 7) Dioctyltin bisoctyl malate

[0098]

The novel polymerization method of the present invention shows high polymerization activity for conjugated diene compounds, and the resulting polymer has a narrow molecular weight distribution, so that it has excellent wear resistance and mechanical properties. It can be widely used industrially as a method for producing a conjugated diene polymer.

Claims (2)

[Claims] 1. The conjugated diene-based compound is represented by the following (a) to
(D) A method for producing a conjugated diene-based polymer, wherein the polymerization is carried out using a catalyst containing a component as a main component. (A) component; a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a compound obtained by reacting these compounds with a Lewis base (b) component; alumoxane (c) component; AlR ¹ R ² R ³ (In the formula, R ^{1 to} R ² are the same or different and are a hydrocarbon group or a hydrogen atom containing 1 to 10 carbon atoms, R ³ is a hydrocarbon group containing 1 to 10 carbon atoms, provided that , R ³ is the above R ¹ or R
Corresponding organic aluminum compound ² may be the same or different from) (d) component; halogenated silicon compound and / or a halogenated organic silicon compound 2. After the polymerization reaction according to claim 1,
At least one selected from the group consisting of the following components (e) to (j)
A method for producing a conjugated diene polymer, comprising reacting a kind of compound. (E) component: R ⁴ _n M′X _4-n , M′X ₄ , M′X ₃ ,
R ⁴ _n M '(-R ⁵ -COOR ⁶ ) _4-n or R
⁴ _n M '(-R ⁵ -COR ⁶ ) _4-n (wherein, R ^{4 to} R ⁵
Are the same or different and are each a hydrocarbon group containing 1 to 20 carbon atoms, R ⁶ is a hydrocarbon group containing 1 to 20 carbon atoms, and contains a carbonyl group or an ester group in the side chain. M ′ is a tin atom, silicon atom, germanium atom or phosphorus atom, X is a halogen atom, n
Is an integer of 0 to 3), a halogenated organometallic compound, a metal halide compound or an organometallic compound (f) component; in the molecule, a Y = C = Z bond (where Y is a carbon atom, A heterocumulene compound containing an oxygen atom, a nitrogen atom or a sulfur atom, and Z is an oxygen atom, a nitrogen atom or a sulfur atom) (g) component; (Wherein, Y 'represents an oxygen atom, a nitrogen atom or a sulfur atom) bonded hetero three-membered ring compound containing a component (h); halogenated isocyano compound of component (i); R ⁷ - (COOH) _m , R ⁸ (CO
^{_{X) m, R 9 - (}} COO-R 10), R 11 -OCOO-R
^{12, R 13 - (COOCO-} R 14) m or ## STR2 ## (Wherein, R ^{7 to} R ¹⁵ are the same or different and each have 1 to 5 carbon atoms)
A hydrocarbon group containing 0 carbon atoms, X is a halogen atom, m
The carboxylic acid corresponding to an a) an integer from 1 to 5, an acid halide, an ester compound, carbonate compound or an acid anhydride (j) _{^{component; R 16 l M "(OCOR}} 17) 4-l, R
¹⁸ _l M "(OCO-R ¹⁹ -COOR ²⁰ ) _4-l , or (In the formula, R ^{16 to} R ²² are the same or different, and have 1 to 2 carbon atoms.
A hydrocarbon group containing 0 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and 1 is an integer of 0 to 3)