JPH09324009A - Catalyst and production of conjugated diene polymer by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conjugated diene having a controlled microstructure in high activity by using a catalyst prepared by combining a specified compound of a group V transition metal in the periodic table with an ionic compound and/or an aluminoxane. SOLUTION: This catalyst comprises a group V transition metal compound represented by the general formula: MR(O)X2 (wherein M is a group V transition metal in the periodic table; R is cyclopentadienyl, a substituted cyclopentadienyl, indenyl, a substituted indenyl, fluorenyl or a substituted fluorenyl; X is hydrogen, a halogen, a 1-20C hydrocarbon group, an alkoxyl or amino) and an ionic compound of a non-coordinative anion with a cation and/or an aluminoxane. Monomers which can be polymerized by using this catalyst are exemplified by α-olefins, cycloolefins and conjugated olefins. Among them, conjugated diene compound monomers are particularly desirable.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel Group V transition metal compound-based catalyst of the periodic table and a method for producing a polymer of a conjugated diene using the catalyst.

[0002]

2. Description of the Related Art Conjugated dienes are known to give polymers having various microstructures by using a polymerization catalyst. In particular, polybutadiene containing a 1,2-structure moderately in a high cis structure is expected to be an impact modifier for a vinyl aromatic polymer.

As a polymerization catalyst for butadiene, a catalyst system using a vanadium compound is known. For example, Chim.
. e Ind, 40, 362 ( 1958) on the like, VCl ₃ as catalyst -
Although a method using AlR ₃ has been reported, crystalline polybutadiene close to 100% trans is obtained, and the polymerization activity is extremely poor.

Further, Macromol. Chem. Phys., 195, 1389
(1994) and others report a method using V (acac) ₃ -methylalumoxane as a catalyst, but polybutadiene of trans 99% or more has been obtained although the catalytic activity is improved.

[0005] Polymer Preprints, Japan 43, 1708 (19
94) is a catalyst system of the same type, with cis 63%, trans 14%, 1,2
-21% polybutadiene reported, but with low activity. Japanese Patent Publication No. 47-1212 discloses that VO (O
R) Polymerization of butadiene with a catalyst system consisting of a vanadium compound such as ₃ -trialkylaluminum-water is disclosed, but with low activity.

On the other hand, as the polymerization of butadiene using a metallocene compound, for example, Macromol. Symp., 89,
383 (1995) reports CpTiCl ₃ (cyclopentadienyltitanium trichloride) -methylalumoxane, but has extremely low polymerization activity.

As for the polymerization of butadiene using a transition metal compound containing two cyclopentazinyl groups (Cp), for example, Cp ₂ is described in Polymers, Vol. 31, 759 (1974).
Polymerization of butadiene using Ni, Cp ₂ TiCl ₂ and Cp ₂ ZrCl ₂ has been performed to obtain a polymer with a high trans content. But,
These catalyst systems have the problem of low activity.

As a polymerization catalyst using a metallocene compound of vanadium metal, for example, Japanese Patent Publication No. 4-41166 describes bis (cyclopentadienyl) vanadium dichloride. It relates to (co) polymerization and does not describe polymerization of conjugated dienes. Also, Table 1-50
Japanese Patent No. 1633 discloses an example of bis (cyclopentadienyl) vanadium dichloride, which relates to a copolymer of ethylene-butadiene.

Japanese Patent Publication No. 46-20494 discloses a method for producing polybutadiene using a catalyst system comprising a cyclopendienyl complex of vanadium, a halogen-containing organoaluminum and an oxygen-containing compound. CpVCl ₃ is exemplified as a cyclopentadienyl complex of vanadium, but has a problem of low polymerization activity. Further, it is essential that the organic aluminum of the co-catalyst contains a halogen component.

Further, JP-A 64-66216 and JP-A-63-50196
No. 2 and Japanese Patent Publication No. 1-501633 disclose a copolymerization catalyst of an olefin and a diene, which is a combination of a vanadium metallocene compound and an alumoxane. They are,
Although bis (cyclopentadienyl) vanadium dichloride ^{_{[(η 5 C 5 H 5}} ) 2 VCl 2] is exemplified as a vanadium metallocenes, there is no description of embodiments using the same.

In Japanese Patent Publication No. 7-509016, an ionizing agent and poly
Having an imide as an anion auxiliary ligand [(η^FiveC_FiveH_Five) VC
l_TwoN (p-CH_Three-C₆H_Four)] Or with a carbolide (η^FiveC
_Five(CH _Three)_Five) (C_TwoB₉H₁₁) Ta (CH_Three)_TwoCatalyst systems such as
However, in all cases, there is a description of polymerization or copolymerization of conjugated diene.
Absent.

It is known that a conjugated diene can be obtained as a polymer having various microstructures by a polymerization catalyst. In particular, polybutadiene containing a 1,2-structure in a high cis structure is expected to be an impact resistance-imparting agent for vinyl aromatic polymers such as polystyrene. Until now, polybutadiene for impact-resistant polystyrene has been known to be based on a butyllithium-based catalyst, but has a high viscosity because it has a smaller cis structure content than polybutadiene obtained from a cobalt-based catalyst. As the cobalt-based catalyst system, JP-A-55-129403 and 59-232106 disclose catalyst systems consisting of phosphate, organoaluminum, water, cobalt compound, organoaluminum, water, cobalt dithiocarbamate compound. A catalyst system consisting of is disclosed. However, the activity is not sufficient.

[0013]

[PROBLEMS TO BE SOLVED] To provide a novel Group V transition metal compound-based polymerization catalyst for the periodic table, and a method for producing a controlled conjugated diene polymer with high activity using the polymerization catalyst. With the goal.

[0014]

The present invention provides (A) a general formula MR (O) X ₂ (wherein M represents a group V transition metal of the periodic table, R represents a cyclopentadienyl group, a substituted group). A cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, X is hydrogen,
Halogen, hydrocarbon group having 1 to 20 carbon atoms, alkoxy group or amino group. And a catalyst obtained from (B) an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane.

The present invention also relates to a catalyst comprising the above-mentioned components (A) and (B).

The present invention also relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using the above catalyst.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the catalyst of the present invention is a group V transition metal compound of the periodic table represented by the general formula MRX ₃ . In the general formula MRX ₃ , M is the periodic table
It is a Group V transition metal. Specifically, the periodic table Va of vanadium (V), niobium (Nb), tantalum (Ta), etc.
Group transition metal, preferably vanadium.

R is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group,
A fluorenyl group or a substituted fluorenyl group is shown.

Substituents in the substituted cyclopentadienyl group, substituted indenyl group or substituted fluorenyl group include methyl group, ethyl group, propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group. And a hydrocarbon group 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, those in which a cyclopentadienyl ring is partially bonded to X by a cross-linking group such as dimethylsilyl, dimethylmethylene, methylphenylmethylene, diphenylmethylene, ethylene and substituted ethylene are also included.

Specific examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group and 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-tetra Methylcyclopentadienyl 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.

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

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

Of the above, R is preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an indenyl group, a 1,2,3-trimethylindenyl group or the like.

X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or an amino group. Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the hydrocarbon substituent having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl,
Examples thereof include a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group such as butyl and t-butyl, and an aromatic hydrocarbon group 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 MR (O) X ₂ of the component (A), a vanadium compound of VR (O) X ₂ in which M is vanadium is preferable.

Specific compounds of the general formula MR (O) X ₂ of the present invention include cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclopentadienyl). Oxovanadium dichloride, (1-methyl
-3-butylcyclopentadienyl) oxovanadium dichloride, (pentamethylcyclopentadienyl) oxovanadium dichloride, (trimethylsilylcyclopentadienyl) oxovanadium dichloride,
(1,3-di (trimethylsilyl) cyclopentadienyl)
Examples thereof include oxovanadium dichloride, indenyloxovanadium dichloride, (2-methylindenyl) oxovanadium dichloride, (2-trimethylsilylindenyl) oxovanadium dichloride, and fluorenyloxovanadium dichloride. Also included are dimethyl compounds in which the chlorine atom of each of the above compounds is replaced with a methyl group.

Those in which R and X are bound by a hydrocarbon group or a silyl group are also included. For example, (t-butylamide)
Dimethyl (eta ⁵ - cyclopentadienyl) silane oxovanadium chloride, (t-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) chlorine atoms of the silane amide chloride of such oxo vanadium chloride, or these compounds Is substituted with a methyl group.

Cyclopentadienyloxovanadium dimethoxide, cyclopentadienyloxovanadium diiso-propoxide, cyclopentadienyloxovanadium diter-butoxide, cyclopentadienyloxovanadium diphenoxide, cyclopentadienyloxo Vanadium methoxy chloride, cyclopentadienyl oxo vanadium iso-propoxycyclolide,
Cyclopentadienyloxovanadium ter-butoxycyclolide, cyclopentadienyloxovanadium phenoxycyclolide and the like can be mentioned. Also included are dimethyl compounds in which the chlorine atom of each of the above compounds is replaced with a methyl group.

(Cyclopentadienyl) (bisdiethylamido) oxovanadium, (Cyclopentadienyl)
(Bisdi-iso-propylamido) oxovanadium, (cyclopentadienyl) (bisdi-n-octylamido) oxovanadium and the like.

In the component (B) of the present invention, the non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation is preferably a bulky one, for example, tetra (phenyl) borate, 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, tridecahydride-7,8-dicarboundecaborate, tetrafluoroborate, hexafluorophosphate and the like can be mentioned.

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. Also, (alkyl) ₂ N (C ₆ H ₅ ) H
N, N-dialkylanilinium cation having an active proton such as ⁺ , trialkylammonium cation,
Triallyl phosphonium cation, trisubstituted carbonium cation such as (C ₆ H ₅ ) ₃ C ⁺ , oxonium cation,
Examples thereof include a sulfonium cation, a carborane cation, a metal carborane cation, a ferrocenium cation having a transition metal, a cation of a main element metal, a transition metal, and a cation to which ether, amine or the like is coordinated.

Specific examples of the carbonium cation include:
Examples include tri-substituted carbonium cations such as triphenyl carbonium cation and tri-substituted phenyl carbonium cation. Specific examples of tri-substituted phenyl carbonium cations include tri (methylphenyl)
Carbonium cation and tri (dimethylphenyl) carbonium cation can be mentioned.

Specific examples of ammonium cations include:
Trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, N, N-diethylanilinium cation, N, N-2,4,6 -
Mention may be made of N, N-dialkylanilinium cations such as pentamethylanilinium cation, di (i-propyl) ammonium cation, dialkylammonium cations such as dicyclohexylammonium cation.

Specific examples of the phosphonium cation include:
Examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

The ionic compound can be preferably used by arbitrarily selecting and combining from the non-coordinating anions and cations exemplified above.

Among them, as the ionic compound, trityl tetra (pentafluorophenyl) borate, triphenylcarbonium tetra (fluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, 1,1 ' -Dimethylferrocenium tetra (pentafluorophenyl) borate and the like are preferable. 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 includes a chain aluminoxane represented by the general formula (—Al (R ′) O—) _n or a cyclic aluminoxane. (R 'is a hydrocarbon group having 1 to 10 carbon atoms and includes those partially substituted with a halogen atom and / or an alkoxy group. N is a degree of polymerization and is 5 or more, preferably 10 or more) . Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an 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.

As the condensing agent, water can be mentioned as a typical one, but in addition to this, an arbitrary one with which the trialkylaluminum undergoes a condensation reaction, for example, adsorbed water such as an inorganic substance or a diol can be mentioned.

In the present invention, the component (A) and the component (B)
In addition to component (C), Periodic Tables I to III
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 triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, boron trifluoride and triphenyl boron.

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 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 group V transition metal compound of the component (A) to the aluminoxane of the component (B) is preferably 1: 1 to. 1: 10000, more preferably 1: 1 to 1:50
00. The molar ratio of the group V transition metal compound of the component (A) to the ionic compound of the component (B) is preferably 1: 0.1 to 1:10, more preferably 1: 0.2 to 1: 5.
It is.

The molar ratio of the group V transition metal compound of the component (A) to the organometallic compound of the component (C) is preferably from 1: 0.1 to 1: 1000, more preferably from 1: 0.2.
It is 1: 500. In the present invention, each catalyst component can be used by being supported on an inorganic compound or an organic polymer compound.

As the inorganic compound as a carrier, inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonates and sulfates can also be used. Particularly preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia. These inorganic oxides have an average particle size of 5 to 15
Porous fine particles having a particle size of 0 μm and a specific surface area of 2 to 800 m ² / g are preferable, and can be used after being heat-treated at, for example, 100 to 800 ° C.

The organic polymer compound is preferably one having an aromatic ring, a substituted aromatic ring or a functional group such as a hydroxy group, a carboxyl group, an ester group or a halogen atom in the side chain. As specific examples, ethylene, propylene, α-olefin homopolymer having the functional group by chemical modification such as polybutene, α-olefin copolymer, acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, homopolymer such as divinylbenzene, Copolymers and their chemically modified products can be mentioned. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 μm are used.

The order of adding the catalyst components is not particularly limited, but, for example, the following order may be adopted. 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 (B) and the component (C) are added in an arbitrary order. The component (B) and then the component (A) are added to a contact mixture of the conjugated diene compound monomer to be polymerized and the component (C). A mixture in which the component (A) and the component (B) are brought into contact in an arbitrary order is added to the conjugated diene compound monomer to be polymerized. To the conjugated diene compound monomer to be polymerized, a mixture in which the component (A), the component (B) and the component (C) are brought into contact in an arbitrary order is added.

The monomer which can be polymerized by using the catalyst in the present invention is not particularly limited, such as α-olefin, cyclic olefin, conjugated diene, and the conjugated diene compound monomer is particularly preferable.

As the conjugated diene compound monomer, 1,3-
Butadiene, isoprene, 1,3-pentadiene, 2-ethyl
-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene and the like can be mentioned. These monomer components may be used alone or in combination of two or more.

The conjugated diene compound monomer to be polymerized here may be the whole amount or a part thereof. In the case of some of the monomers, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution. Besides conjugated dienes, ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, 4-methylpentene-
1, non-cyclic monoolefins such as hexene-1, octene-1, cyclic monoolefins such as cyclopentene, cyclohexene and norbornene, and / or aromatic vinyl compounds such as styrene and α-methylstyrene, dicyclopentadiene, 5-ethylidene It may contain a small amount of non-conjugated diolefin such as 2-norbornene and 1,5-hexadiene.

The polymerization method is not particularly limited, and bulk polymerization,
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; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; -Butene, cis-2-butene, trans-2-
Olefinic hydrocarbons such as butene, mineral spirits, solvent naphtha, hydrocarbon solvents such as kerosene,
Halogenated hydrocarbon solvents such as methylene chloride are exemplified. Further, 1,3-butadiene itself may be used as the polymerization solvent.

Among them, toluene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is 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 -100 to 150 ° C, more preferably -100 to 100 ° C, and -50 to 100 ° C.
Is even more preferable, and a range of -50 to 60 ° C is particularly preferable.

The polymerization time is preferably in the range of 10 minutes to 12 hours, particularly preferably 30 minutes to 6 hours.

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

When a conjugated diene is polymerized using the catalyst of the present invention, the microstructure of the resulting polymer is controlled. The content of the cis structure is usually 40 to 97% by weight, preferably 80 to 95% by weight, particularly preferably 85 to 92% by weight. The content of the vinyl structure is usually 3 to 60% by weight, preferably 5 to 20% by weight, particularly preferably 8 to 15% by weight. Therefore, it is also useful as a diene polymer for producing high impact polystyrene.

[0061]

EXAMPLES In the examples, "catalytic activity" is the polymer yield (g) per 1 hour of polymerization time per 1 mmol of transition metal of the transition metal compound catalyst used in the polymerization reaction.
The molecular weight distribution was determined using GP using polystyrene as a standard.
Ratio of weight average molecular weight Mw and number average molecular weight Mn obtained from C
Evaluated by Mw / Mn. Microstructure was performed by infrared absorption spectroscopy. Cis 740 cm ^-1 , transformer 980
The microstructure was calculated from the absorption intensity ratio of cm ⁻¹ and vinyl 910 cm ⁻¹ .

(Synthesis Example) [Preparation of Transition Metal Compound] Organometallics 1988, 7, 4
Vanadium oxy (cyclopentadienyl) dichloride: VCp (O) Cl ₂ was synthesized according to the synthesis method on pages 96-502, and prepared as a catalyst solution using toluene as a solvent.

Example 1 [Butadiene polymerization] To 200 ml of toluene, 1 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.) was added as a toluene solution, and the solution was kept at 40 ° C. 32 ml of butadiene was added, 1 μmol of the above transition metal compound was added as a toluene solution, and polymerization was carried out for 1 hour. Polymerization was stopped with an ethanol solution containing HCl, filtered and dried to obtain a white butadiene polymer. The catalytic activity was 6,200 (g / mmol.Mh).
Micro structure is cis 89.9%, transformer 1.8%, vinyl 8.3
% Met. The weight average molecular weight is 2,540,000, Mw /
The Mn was 2.06.

Example 2 [Butadiene polymerization] Polymerization was carried out in the same manner as in Example 2 except that 2 mmol of the above methylalumoxane was used. As a result, a butadiene polymer was obtained. The catalytic activity is 7,500 (g / mmo
lMh). Micro structure is cis 89.9%, transformer
It was 1.6% and vinyl 8.5%. The weight average molecular weight was 2,730,000 and Mw / Mn was 3.34.

Example 3 [Butadiene Polymerization] Polymerization was carried out in the same manner as in Example 2 except that 5 mmol of the above methylalumoxane was used. As a result, a butadiene polymer was obtained. The catalytic activity is 9,000 (g / mmo
lMh). Micro structure is cis 89.9%, transformer
It was 1.6% and vinyl 8.5%. The weight average molecular weight was 2,826,000 and Mw / Mn was 2.82.

Example 4 [Polymerization of butadiene] 0.2 mmol of triisobutylaluminum was added as a toluene solution to 200 ml of toluene, and the solution was kept at 40 ° C. After adding 32 ml of butadiene, [Ph ₃ CB
(C ₆ F ₅ ) ₄ ], 1.5 μmol, the above transition metal compound 1.0 μmol
Was added as a toluene solution, and polymerization was carried out for 1 hour. H
Polymerization was stopped with a Cl-containing ethanol solution, followed by filtration and drying to obtain a white butadiene polymer. Catalytic activity is 10,200 (g
/mmol.Mh). The microstructure was cis 88.9%, trans 1.7%, and vinyl 9.4%. The weight average molecular weight was 2,917,000 and Mw / Mn was 2.96.

Example 5 [Butadiene polymerization] To 200 ml of toluene, 0.2 mmol of triisobutylaluminum was added as a toluene solution, and the solution was kept at 40 ° C. After adding 32 ml of butadiene, [Ph ₃ CB
1.5 μmol of (C ₆ F ₅ ) ₄ ] was added, and 1.0 μmol of the above transition metal compound was added as a toluene solution while introducing hydrogen at a rate of 5 ml / min., And polymerization was carried out for 1 hour. Polymerization was stopped with an ethanol solution containing HCl, filtered and dried to obtain a white butadiene polymer. The catalytic activity is 8,100 (g / mmol.M.
h). Micro structure is cis 87.2%, transformer 3.6%,
It was 9.2% vinyl. The weight average molecular weight is 502,000.
0 and Mw / Mn were 1.59.

Example 6 [Butadiene polymerization] Polymerization was carried out under the same conditions as in Example 6 except that hydrogen was introduced at a rate of 20 ml / min. HC
Polymerization was stopped with a 1-containing ethanol solution, filtered and dried to obtain a white butadiene polymer. The catalytic activity is 5,200 (g / m
mol.Mh) microstructure is cis 86.7%, trans 5.
It was 9% and 7.4% vinyl. The weight average molecular weight is 1
9,000 and Mw / Mn were 2.86.

Comparative Example 1 [Butadiene Polymerization] Polymerization was performed in the same manner as in Example 2 except that 1.0 μmol of vanadium trichloride (VOCl ₃ ) was used as the above transition metal compound. As a result, substantially no polymer was obtained.

Comparative Example 2 [Butadiene Polymerization] Polymerization was carried out in the same manner as in Example 4 except that 1.0 μmol of vanadium trichloride (VOCl ₃ ) was used as the above transition metal compound. As a result, substantially no polymer was obtained.

Example 7 The inside of an autoclave having an internal capacity of 1.5 L was replaced with nitrogen, and 300 mL of toluene and butadiene were used.
Charged 62g. Next, 0.75 mmol of triethylaluminum as the component (C), 0.0075 mmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) as the component (B), and as the component (A) Vanadium oxy (cyclopentadienyl) dichloride: VCp (O) Cl ₂ was added at 0.005 mmol and the polymerization temperature was 40 ℃.
Polymerization was performed for minutes. Table 2 shows the polymerization results.

(Examples 8 to 10) Example 8 was repeated except that the conditions shown in Table 1 were used. Table 2 shows the polymerization results.

(Examples 11 to 12) The same procedure as in Example 7 was carried out except that cyclohexane was used instead of toluene as the polymerization solvent and the conditions were as shown in Table 1. Table 2 shows the polymerization results.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

The present invention provides a method for producing a conjugated diene polymer having a controlled microstructure with high activity by using a novel polymerization catalyst. In particular, butadiene provides a new catalyst system for the production of polymers with controlled vinyl structure.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Jun Yamashita 8-1 Goi Minamikaigan, Ichihara-shi, Chiba Ube Industries Ltd. Polymer Research Laboratory (72) Nobuhiro Tsujimoto 8th Goi Minamikaigan, Ichihara-shi, Chiba No. 1 Ube Industries, Ltd., Polymer Research Laboratory

Claims (3)

[Claims] 1. (A) General formula MR (O) X ₂ (wherein M represents a group V transition metal of the periodic table, and R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group. , A substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, and X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or an amino group. A catalyst obtained from a compound, (B) an ionic compound of a non-coordinating anion and a cation, and / or an aluminoxane. 2. The component (A) and the component (B) according to claim 1.
A catalyst consisting of components. 3. A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using the catalyst according to claim 1. Description: