JP2001064315A - Polymerization of conjugated diene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conjugated diene polymer in high catalytic activity by polymerizing a conjugated diene in the presence of a catalyst obtained from a metallocene type complex of a transition metal compound and an ionic compound between a non-coordinatable anion and a cation, and/or an aluminoxane. SOLUTION: A catalyst is obtained by combining a metallocene type complex of a transition metal compound of the formula: MRX3 with an ionic compound composed of a non-coordinatable anion and a cation, and/or an aluminoxane. A conjugated diene represented by the formula is polymerized at -100 to 100 deg.C for 1 min to 24 hr in the presence of the catalyst. The solvent used in a solution polymerization is desirably toluene or cyclohexane. In the formula, R1 is a 1-8C hydrocarbon group; R2 and R3 are each H or a 1-8C hydrocarbon group; M is a transition metal of group V in the periodic table; R is cyclopentadienyl, indenyl, a substituterd indenyl, fluorenyl, or a substituted fluorenyl; and X is H, a halogen, a 1-20C hydrocarbon group, an alkoxy, or amino.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a conjugated diene polymer having a specific structure.

[0002]

2. Description of the Related Art A catalyst system using a metallocene-type vanadium compound as a conjugated diene polymerization catalyst is known.
For example, JP-A-9-291108 discloses a general formula V
RX ₃ (wherein, R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group;
Represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or an amino group. ), And (B) a method of polymerizing a conjugated diene using a catalyst obtained from an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane. As the polymerizable conjugated diene, butadiene, isoprene, 1,3-pentadiene and the like are described,
As a specific example, only butadiene is described. Conjugated dienes such as 1,3-pentadiene have cis- and trans-isomers, but their polymerization behavior is not specifically described.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a conjugated diene polymer having a specific structure with high activity using a metallocene-type transition metal compound-based polymerization catalyst.

[0004]

The present invention uses (A) a metallocene complex of a transition metal compound, and (B) a catalyst obtained from an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane. And producing a conjugated diene polymer represented by the general formula (1).

Embedded image (In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.)

In the present invention, the metallocene complex of the transition metal compound (A) is represented by the general formula MRX ₃ (where M represents a transition metal of Group V of the periodic table, and R represents a cyclopentadienyl group) A substituted cyclopentadienyl group, an indenyl group,
X represents a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, and X represents hydrogen, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or an amino group. The present invention relates to a method for producing the above conjugated diene polymer, which is a transition metal compound represented by the following formula:

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the catalyst of the present invention is a metallocene complex of a transition metal compound.
Is a Group V transition metal compound Periodic Table represented by the general formula MRX _3.

In the general formula MRX ₃ , M is a transition metal belonging to Group V of the periodic table. Specifically, it is a transition metal of Group Va in the periodic table such as vanadium (V), niobium (Nb), or tantalum (Ta), and is preferably vanadium.

R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group,
It represents a fluorenyl group or a substituted fluorenyl group.

The substituent in the substituted cyclopentadienyl group, the substituted indenyl group or the substituted fluorenyl group includes methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl. And hydrocarbon groups containing a silicon atom such as a group, a t-butyl group, a hexyl group, a phenyl group, a benzyl group and a trimethylsilyl group. Further, a cyclopentadienyl ring is part of X and dimethylsilyl, dimethylmethylene, methylphenylmethylene, diphenylmethylene,
Also included are those linked by a crosslinking group such as ethylene and substituted ethylene.

Specific examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,3-di ( t-butyl) cyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, 1
-Ethyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-benzyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-phenyl-2,
3,4,5-tetramethylcyclopentadienyl group,
1-trimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trifluoromethyl-
2,3,4,5-tetramethylcyclopentadienyl group and the like.

Specific examples of the substituted indenyl group include 1,1
Examples include a 2,3-trimethylindenyl group, a heptamethylindenyl group, a 1,2,4,5,6,7-hexamethylindenyl group.

Specific examples of the substituted fluorenyl group include a methylfluorenyl group.

Among the above, R represents cyclopentadienyl group, methylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 1,2,3
-A trimethylindenyl group and the like are preferred.

X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or an amino group.

Specific examples of halogen include a fluorine atom,
Examples include a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the hydrocarbon substituent having 1 to 20 carbon atoms include straight-chain aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl or branched aliphatic hydrocarbon groups. And aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl and benzyl. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included. Among them, methyl, benzyl, trimethylsilylmethyl and the like are preferable.

Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, propoxy, butoxy and the like. Further, amyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, thiomethoxy and the like may be used.

Specific examples of the amino group include dimethylamino, diethylamino, diisopropylamino and the like.

Among the above, X is a fluorine atom,
Chlorine, bromine, methyl, ethyl, butyl,
A methoxy group, an ethoxy group, a dimethylamino group, a diethylamino group and the like are preferable.

In the general formula MRX ₃ of the component (A), M
Is a vanadium compound of VRX _{3 wherein} is vanadium.

In the present invention, specific compounds of VRX ₃ include the following (1) to (18).

(1) Cyclopentadienyl vanadium trichloride.

(2) Monosubstituted cyclopentadienyl vanadium trichloride, for example, methylcyclopentadienyl vanadium trichloride, ethylcyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, isopropylcyclopentadienyl Vanadium trichloride, t-butylcyclopentadienyl vanadium trichloride, benzylcyclopentadienyl vanadium trichloride, (1,1-dimethylpropyl) cyclopentadienyl vanadium trichloride, (1,1-dimethylbenzyl) cyclopenta Dienyl vanadium trichloride, (1-ethylpropyl) cyclopentadienyl vanadium trichloride, (1-ethyl, 1-methylpropyl) cyclo Pentadienyl vanadium trichloride, (diethylbenzyl) cyclopentadienyl vanadium trichloride, (trimethylsilylcyclopentadienyl) vanadium trichloride, (bis (trimethylsilyl) cyclopentadienyl) vanadium trichloride and the like can be mentioned.

(3) 1,3-disubstituted cyclopentadienyl vanadium trichloride, for example, (1,3-dimethylcyclopentadienyl) vanadium trichloride, (1-methyl-3-ethylcyclopentadienyl) Vanadium trichloride, (1-methyl-3-
Propylcyclopentadienyl) vanadium trichloride, (1-methyl-3-bis (trimethylsilyl)
(Silylcyclopentadienyl) vanadium trichloride, (1-methyl-3-phenylcyclopentadienyl) vanadium trichloride, (1-methyl-3-
(Tolylcyclopentadienyl) vanadium trichloride, (1-methyl-3- (2,6-dimethylphenyl) cyclopentadienyl) vanadium trichloride, (1-methyl-3-butylcyclopentadienyl) vanadium trichloride And the like.

(4) 1,2,3-trisubstituted cyclopentadienyl vanadium trichloride, for example, (1,
(2,3-trimethylcyclopentadienyl) vanadium trichloride, (1,2,3-triethylcyclopentadienyl) vanadium trichloride, (1,2,3
-Triphenylcyclopentadienyl) vanadium trichloride.

(5) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride, for example (1,
(2,4-trimethylcyclopentadienyl) vanadium trichloride, (1,2,4-triethylcyclopentadienyl) vanadium trichloride, (1,2,4
-Triphenylcyclopentadienyl) vanadium trichloride.

(6) Tetra-substituted cyclopentadienyl vanadium trichloride, for example, (1,2,3,4
-Tetramethylcyclopentadienyl) vanadium trichloride, (1,2,3,4-tetraphenylcyclopentadienyl) vanadium trichloride and the like.

(7) penta-substituted cyclopentadienyl vanadium trichloride, for example, (pentamethylcyclopentadienyl) vanadium trichloride,
(1,2,3,4-tetramethyl-5-phenylcyclopentadienyl) vanadium trichloride, (1,
2,3,4-tetraphenyl-5-methylcyclopentadienyl) vanadium trichloride, (pentaphenylcyclopentadienyl) vanadium trichloride, and the like.

(8) Indenyl vanadium trichloride.

(9) Substituted indenyl vanadium trichloride, for example, (2-methylindenyl) vanadium trichloride, (2-trimethylsilylindenyl) vanadium trichloride and the like.

(10) Monoalkoxides and dialkoxides in which the chlorine atoms of the compounds of the above (1) to (9) are partially substituted with alkoxy groups. For example, cyclopentadienyl vanadium t-butoxide dichloride, cyclopentadienyl vanadium iso-propoxide dichloride, cyclopentadienyl vanadium dimethoxy chloride, cyclopentadienyl vanadium diiso-propoxycyclolide, cyclopentadienyl vanadium Di-tert-butoxychloride, cyclopentadienyl vanadium diphenoxycyclolide, cyclopentadienyl vanadium iso-propoxy dichloride, cyclopentadienyl vanadium ter-butoxy dichloride, cyclopentadienyl vanadium phenoxy dichloride and the like can be mentioned.

(11) Methyl, dimethyl and trimethyl forms in which the chlorine atom in the above (1) to (10) is substituted by a methyl group.

(12) R is bonded to X by a hydrocarbon group or a hydrocarbon silyl group. For example, (t-butylamido) dimethylsilyl (η5-cyclopentadienyl) vanadium dichloride, (t-butylamido) dimethylsilyl (trimethyl-η5-cyclopentadienyl) vanadium dichloride,
Butylamido) dimethylsilyl (tetramethyl-η5-
(Cyclopentadienyl) vanadium dichloride.

(13) Methyl and dimethyl compounds obtained by substituting the chlorine atom of the above (12) with a methyl group are mentioned.

(14) Monoalkoxy and dialkoxy compounds obtained by substituting the chlorine atom of the above (12) with an alkoxy group are mentioned.

(15) Compounds obtained by substituting the monochloro compound of the above (14) with a methyl group.

(16) An amide in which the chlorine atom in the above (1) to (10) is substituted by an amide group. For example, (cyclopentadienyl) (tris-diethylamido) vanadium, (cyclopentadienyl) (tris-i
(so-propylamido) vanadium, (cyclopentadienyl) (tris-n-octylamido) vanadium,
(Cyclopentadienyl) (bisdiethylamide) vanadium chloride, (cyclopentadienyl) (bisi
(so-propylamido) vanadium chloride, (cyclopentadienyl) (bis-n-octylamido) vanadium chloride, (cyclopentadienyl) (diethylamido) vanadium dichloride, (cyclopentadienyl) (iso-propylamido) vanadium dichloride , (Cyclopentadienyl) (n-octylamide) vanadium dichloride and the like.

(17) Fluorenyl vanadium trichloride, methylfluorenyl vanadium trichloride and the like can be mentioned. Further, a compound in which a chlorine atom is substituted by a methyl group, an alkoxy group, or an amide group is also exemplified.

Among them, cyclopentadienyl vanadium trichloride, methylcyclopentadienyl vanadium trichloride, pentamethylcyclopentadienyl vanadium trichloride, indenyl vanadium trichloride, 1,2,3-trimethylindenyl vanadium trichloride , Cyclopentadienyl vanadium tri (methoxide), pentamethylcyclopentadienyl vanadium tri (methoxide) and the like are preferably used.

In the component (B) of the present invention, the non-coordinating anion constituting the ionic compound of a non-coordinating anion and a cation is, for example, tetra (phenyl) borane.
, Tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, Tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate And tridecahydride-7,8-dicarbaundecaborate.

On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

Specific examples of the carbonium cation include:
Examples include trisubstituted carbonium cations such as triphenylcarbonium cation and trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include tri (methylphenyl)
Examples thereof include a carbonium cation and a tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include:
Trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl)
Trialkylammonium cations such as ammonium cation, N, N-diethylanilinium cation,
Examples thereof include N, N-dialkylanilinium cations such as N, N-2,4,6-pentamethylanilinium cation, dialkylammonium cations such as di (iso-propyl) ammonium cation, and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include:
Triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation can be mentioned.

As the ionic compound, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

Among the ionic compounds, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) Phenyl)
Borates and 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate are preferred.

The ionic compounds may be used alone or in combination of two or more.

Alumoxane may be used as the component (B) of the present invention. The alumoxane is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (-Al (R ') O-) n
Or a cyclic aluminoxane represented by the following formula: (R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization and is 5 or more, preferably 10 or more.) . Examples of R ′ include a methyl, ethyl, propyl, and isobutyl group, and a methyl group is preferable. Examples of the organoaluminum compound used as a raw material of the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

Alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used. In particular, alumoxane having good solubility in aliphatic hydrocarbons is preferable.

Examples of the condensing agent include water, which is a typical one. In addition, any condensing agent capable of condensing the trialkylaluminum, for example, adsorbed water such as inorganic substances, diol, etc. .

In the present invention, the components (A) and (B)
To the periodic table I-III as component (C).
The polymerization of the conjugated diene may be performed by combining an organometallic compound of a group element. The addition of the component (C) has the effect of increasing the polymerization activity. Examples of the organometallic compounds of Group I to III elements of the periodic table include organoaluminum compounds, organolithium compounds, organomagnesium compounds, organozinc compounds, and organoboron compounds.

Specific compounds include methyllithium, butyllithium, phenyllithium, benzyllithium, neopentyllithium, trimethylsilylmethyllithium, bistrimethylsilylmethyllithium, dibutylmagnesium, dihexylmagnesium, diethylzinc, dimethylzinc, trimethylaluminum, Examples thereof include triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, boron trifluoride, and triphenylboron.

Further, ethyl magnesium chloride,
Organometallic halides such as butylmagnesium chloride, dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride and the like, and hydrogenated organometallic compounds such as diethylaluminum hydride and sesquiethylaluminum hydride are also included. Further, two or more kinds of organometallic compounds can be used in combination.

When an ionic compound is used as the component (B), the above alumoxane may be used in combination as the component (C).

The mixing ratio of each catalyst component varies depending on various conditions, but the molar ratio of the transition metal compound of Group V of the Periodic Table (A) to the aluminoxane of the component (B) is preferably 1: 1 to 1: 1. 1: 10000, more preferably 1: 1
１ ： 1: 5000.

The molar ratio of the transition metal compound belonging to Group V of the Periodic Table (A) to the ionic compound (B) is preferably from 1: 0.1 to 1:10, and more preferably from 1: 0. .2
１ ： 1: 5.

The molar ratio of the transition metal compound of Group V of the Periodic Table (A) to the organometallic compound of the component (C) is preferably from 1: 0.1 to 1: 1000, more preferably from 1: 1,000.
0.2 to 1: 500.

The order of addition of the catalyst component is not particularly limited, but can be, for example, in the following order. The component (A) is added to a contact mixture of the conjugated diene compound monomer to be polymerized and the component (B). The component (A) is added to a contact mixture in which the conjugated diene compound monomer to be polymerized, the component (C) and the alumoxane of the component (B) are added in any order. The ionic compound (B) and then the component (A) are added to the contact mixture of the conjugated diene compound monomer to be polymerized and the component (C). (A) The contact mixture of the conjugated diene compound monomer to be polymerized and the component (C)
The component and then the ionic compound of the component (B) are added.

In the present invention, the catalyst system
Further, water may be added as the component (D).

The catalyst of the present invention and / or each component of the catalyst can be used by being supported on an inorganic compound or an organic polymer compound.

The conjugated diene compound monomer to be polymerized here may be a whole or a part. Monomer
In some cases, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution.

The conjugated diene monomer is a conjugated diene represented by the general formula (1).

Embedded image

(Wherein, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.) R ¹ , R ² And R ³ are a methyl group, an ethyl group, n
-Propyl, iso-propyl, n-butyl, iso-
Butyl, sec-butyl, t-butyl, cyclohexyl, phenyl and the like.

As a specific conjugated diene, trans-
1,3-pentadiene, trans-1,3-hexadiene, trans-1,3-heptadiene, trans-1,
3-octadiene, trans-2-methyl-1,3-pentadiene, trans-2-ethyl-1,3-pentadiene, trans, trans-2,4-hexadiene, trans, trans-2,4-heptadiene, trans,
Trans-2,4-octadiene, trans, trans-3,5-octadiene, trans, trans-2-methyl-2,4-hexadiene, trans, trans-2
-Ethyl-2,4-hexadiene and the like. Examples of the structural formula include the compounds shown below.

[0065]

Embedded image

These monomer components may be used alone or in combination of two or more.

Conjugated dienes other than those represented by the above general formula (1), such as butadiene and isoprene, may be used in combination.

In addition to conjugated dienes, acyclic monoolefins such as ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, 4-methylpentene-1, hexene-1, and octene-1; Cyclopentene,
Cyclic monoolefins such as cyclohexene and norbornene, and / or non-conjugated diolefins such as aromatic vinyl compounds such as styrene and α-methylstyrene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,5-hexadiene; May contain a small amount.

The polymerization method is not particularly limited.
Solution polymerization or the like can be applied. Examples of the solvent in the solution polymerization include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as n-hexane, butane, heptane, and pentane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; Olefinic hydrocarbons such as -butene, cis-2-butene, and trans-2-butene; mineral spirits, solvent naphtha, hydrocarbon solvents such as kerosene, and halogenated hydrocarbon solvents such as methylene chloride. . Alternatively, the polymerization may be performed by bulk polymerization using conjugated dienes themselves as a polymerization solvent.

Among them, toluene, cyclohexane, a mixture of cis-2-butene and trans-2-butene, and the like are preferably used. Bulk polymerization and polymerization using a hydrocarbon solvent having a low boiling point have an advantage that large energy is not required for solvent recovery.

The polymerization temperature is preferably in the range of -100 to 150 ° C, more preferably in the range of -100 to 100 ° C.
The range of 50 to 100 ° C is even more preferred, and -50 to
A range of 60 ° C. is particularly preferred.

The polymerization time is preferably in the range of 1 minute to 24 hours, particularly preferably 5 minutes to 6 hours.

After the polymerization is carried out for a predetermined time, the pressure inside the polymerization tank is released as required, and post-treatments such as washing and drying steps are performed.

[0074]

EXAMPLES Microstructure was performed by ¹ H-NMR analysis. The molecular weight distribution was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn determined by GPC using polystyrene as a standard substance.

(Example 1) The inside of a 50-mL flask was replaced with nitrogen, and 18 mL of well-dried toluene and 2.0 mL of well-dried trans-1,3-pentadiene were added.
I charged. Next, 0.52 mL of a toluene solution of alumoxane (MMAO) (concentration: Al 1.9 mol / L) prepared using a mixture of trimethylaluminum and tributylaluminum as a raw material as the component (B), (A)
As a component, a toluene solution of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) (concentration: 5 mmol of CpVCl ₃ )
1 / L) was added, and polymerization was carried out at a polymerization temperature of 25 ° C. for 6 minutes. The polymerization was stopped with an ethanol solution to which an antioxidant was added. After that, the polymerization liquid is poured into ethanol,
The polymer was precipitated, washed, filtered and dried. Yield 0.
33g, Mw531200, Mn307200, Mw
/1.73, cis 69.5%, trans 1.8%,
vinyl (1,2) 28.7%.

Example 2 The inside of a flask having an internal volume of 50 mL was replaced with nitrogen, and 8 mL of well-dried toluene and 2.3 mL of well-dried trans-2-methyl-1,3-pentadiene were charged. Then, as a component (B), a toluene solution of alumoxane (MMAO) (concentration: Al 1.9 mol / L) prepared using a mixture of trimethylaluminum and tributylaluminum as a raw material, 2.63.
mL, a toluene solution of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) (concentration: CpVCl ₃ ) as the component (A)
5 mmol / L) and a polymerization temperature of 25 ° C.
For 3 hours. The polymerization was stopped with an ethanol solution to which an antioxidant was added. Thereafter, the polymerization solution was poured into ethanol to precipitate the polymer, which was washed, filtered and dried. Yield 1.10 g, Mw 202200, Mn 804
00, Mw / Mn 2.51, cis 87.0%, tra
ns 12.3%, vinyl (3,4) 0.7%.

(Comparative Example 1) The inside of a 50-mL flask was replaced with nitrogen, and 8 mL of well-dried toluene and 2.0 mL of well-dried cis-1,3-pentadiene were charged. Next, as a component (B), a toluene solution of alumoxane (MMAO) prepared using a mixture of trimethylaluminum and tributylaluminum as a raw material (concentration:
Al 1.9 mol / L) as a component (A), and cyclopentadienyl vanadium trichloride (CpVC
l ₃ ) toluene solution (concentration: CpVCl ₃ 5 mmol / L)
Was added and polymerization was carried out at a polymerization temperature of 25 ° C. for 24 hours. The polymerization was stopped with an ethanol solution to which an antioxidant was added. Thereafter, the polymerization liquid was poured into ethanol, but almost no polymer was obtained.

(Comparative Example 2) The inside of a flask having an internal volume of 50 mL was replaced with nitrogen, and 8 mL of well dried toluene and 2.3 mL of well dried cis-2-methyl-1,3-pentadiene were charged. Next, 2.63 m of a toluene solution of alumoxane (MMAO) (concentration: Al 1.9 mol / L) prepared using a mixture of trimethylaluminum and tributylaluminum as a raw material as the component (B).
L, a toluene solution of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) as a component (A) (concentration: CpVCl ₃ 5)
(mmol / L), and polymerization was carried out at a polymerization temperature of 25 ° C. for 24 hours. The polymerization was stopped with an ethanol solution to which an antioxidant was added. Thereafter, the polymerization liquid was poured into ethanol, but almost no polymer was obtained.

[0079]

According to the present invention, it is possible to provide a method for producing a conjugated diene polymer having a specific structure with high activity using a vanadium-based polymerization catalyst system.

Continued on front page F-term (reference) 4J028 AA01A AB00A AC31A AC37A AC38A AC39A BA01A BA01B BA02A BA02B BB01A BB01B BB02A BB02B BC01B BC05A BC05B BC06A BC06B BC09A BC09B BC12A BC12B BC13B BC13B BC BC BC BC BC BC BC BC BC BC BC BC BC EA01 EB02 EB04 EB05 EB06 EB08 EB09 EB10 EB12 EB16 EB17 EB18 EB21 EB26 EC01 EC02 FA01 FA02 FA07 GA01 GA06

Claims (2)

[Claims] (1) using a catalyst obtained from (A) a metallocene complex of a transition metal compound, and (B) an ionic compound of a non-coordinating anion and a cation and / or a catalyst obtained from aluminoxane. A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene represented by the formula (I). Embedded image (In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.) 2. The metallocene of the transition metal compound (A)
Type complex has the general formula MRX _Three (Where M is group V of the periodic table)
R represents a cyclopentadienyl group, a substituted metal,
Clopentadienyl group, indenyl group, substituted indenyl
A fluorenyl group or a substituted fluorenyl group;
Represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms,
It represents a lucoxy group or an amino group. ) Transition metal
The conjugated compound according to claim 1, which is a compound.
A method for producing an ene polymer.