JP2000212193A - Vandium complex composition, catalyst and production of conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition used as a part of a catalyst capable of producing a conjugated diene having controlled micro-structure thereof by mixing a vanadium complex so as to have a specific physical property. SOLUTION: This vanadium complex composition is obtained by mixing the vanadium complex so as to become 0.7-1.8 ratio of the maximum light absorbance Abs (5) at 450-540 nm in its toluene solution to the maximum light absorbance Abs (6) at 550-650 nm, Abs (5)/Abs (6). As the Abs (5), a light absorbance at 511.5 nm in the toluene solution is allowed to be used. As the Abs (6), the light absorbance at 600 nm in the toluene solution is allowed to be used. The composition is preferably a mixture of a compound of the formula: RMX3 [R is a (substituted) cyclopentadienyl; X is a halogen] with a compound of the formula: RM(O)X2 (M is vanadium).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vanadium complex composition, a catalyst, and a method for producing a conjugated diene polymer using the same.

[0002]

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

[0003] Japanese Patent Application Laid-Open No. 9-291108 discloses a
Rhodium metallocene compound RMX _Three And JP-A-9-
JP-A-32409 discloses a general formula RM (O) X_Two (formula
In the formula, M represents vanadium metal, and R represents cyclopentadiene.
X represents a substituted or substituted cyclopentadienyl group;
Indicate Logen. The above polybut using) as a catalyst component
A method for producing tadiene is disclosed. These compounds
Japanese Patent Application Laid-Open No. 10-298230 discloses a synthesis of
RMX_Three RM (O) X_Two 
A method for preparing a series compound is disclosed.
RMX depending on the set conditions or storage conditions of the compound
_Three And RM (O) X_TwoMay be obtained as a mixture of
To determine the physical properties of these mixtures and use them as catalyst components.
I had to be.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a vanadium complex composition having specified physical properties, a catalyst system using the compound as a catalyst component, and an improved conjugated diene polymer having a controlled microstructure. A method for producing with polymerization activity is provided.

[0005]

The present invention relates to a mixture of vanadium complexes, wherein the ratio Abs (5) of the maximum absorbance Abs (5) at 450 to 549 nm of a toluene solution to the maximum absorbance Abs (6) at 550 to 650 nm is used. ) / A
The present invention relates to a vanadium complex composition, wherein bs (6) is 0.7 to 1.8.

In the present invention, the mixture of the above-mentioned vanadium complexes may be composed of RMX ₃ and a general formula RM (O) X ₂ (wherein M represents a vanadium metal, and R represents a cyclopentadienyl group or a substituted cyclopentane). Wherein X represents a dienyl group, and X represents a halogen.).

Further, the present invention is selected from the group consisting of (A) the vanadium complex composition described above, and (B) an ionic compound of a non-coordinating anion and a cation, a Lewis acid compound, and an aluminoxane. It relates to a catalyst comprising at least one compound.

[0008] The present invention also relates to a method for producing a conjugated diene polymer using the above-mentioned catalyst.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The vanadium complex composition of the present invention has a ratio Abs (5) / Abs (5) between the maximum absorbance Abs (5) at 450 to 549 nm and the maximum absorbance Abs (6) at 550 to 650 nm of a toluene solution. 6) is 0.7 to 1.8. As Abs (5), the absorbance at 511.5 nm of a toluene solution may be used. Abs (6) includes the toluene solution 6
The absorbance at 00 nm may be used.

The vanadium complex composition of the present invention mainly comprises RMX ₃ and RM (O) X _2, or RMX ₃ .La and RM (O) X ₂ .La (wherein
M represents a vanadium metal, R represents a cyclopentadienyl group or a substituted cyclopentadienyl group, X represents a halogen, and a is 0, 1, or 2).

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

As the substituent in the substituted cyclopentadienyl group, the substituted indenyl group or the substituted fluorenyl group, methyl, ethyl, propyl, iso-propyl, n
Linear or branched aliphatic hydrocarbon groups such as -butyl, iso-butyl, sec-butyl, t-butyl and hexyl; aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl and benzyl; and trimethylsilyl And other hydrocarbon groups containing a silicon atom. Further, a cyclopentadienyl ring is bonded to a part of X with dimethylsilylene (Me ₂ Si), dimethylmethylene (Me ₂ C),
Methylphenylmethylene (PhMeC), diphenylmethylene (Ph ₂ C), ethylene, also include those bonded at the cross-linking group such as 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 them, 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. Xs may all be the same or different from each other.

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

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl.
A straight-chain or branched aliphatic hydrocarbon group such as -butyl and hexyl; 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 preferred.

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 represents hydrogen, fluorine atom, chlorine atom, bromine atom, methyl, ethyl, butyl,
Preferred are methoxy, ethoxy, dimethylamino, diethylamino and the like.

L is a Lewis base, which is a general Lewis basic inorganic or organic compound capable of coordinating to a metal. Among them, compounds having no active hydrogen are particularly preferred. Specific examples include ethers, esters, ketones, amines, phosphines, silyloxy compounds, olefins, dienes,
Aromatic compounds, alkynes and the like can be mentioned.

Specific compounds represented by RMX ₃ include the following compounds (i) to (xvi).

(I) Cyclopentadienyl vanadium trichloride. Mono-substituted cyclopentadienyl vanadium trichloride, for example, methylcyclopentadienyl vanadium trichloride, ethylcyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, isopropylcyclopentadienyl vanadium trichloride, t- Butylcyclopentadienyl vanadium trichloride, (1,1-dimethylpropyl) cyclopentadienyl vanadium trichloride, (benzyl) cyclopentadienyl vanadium trichloride, (2-
(Phenyl-2-propyl) cyclopentadienyl vanadium trichloride, (3-pentyl) cyclopentadienyl vanadium trichloride, (3-methyl-3-
(Pentyl) cyclopentadienyl vanadium trichloride, (3-phenyl-3-pentyl) cyclopentadienyl vanadium trichloride, (trimethylsilylcyclopentadienyl) vanadium trichloride and the like.

(Ii) 1,2-disubstituted cyclopentadienyl vanadium trichloride such as (1,2-
(Dimethylcyclopentadienyl) vanadium trichloride, (1-ethyl-2-methylcyclopentadienyl) vanadium trichloride, (1-methyl-2-propylcyclopentadienyl) vanadium trichloride, (1-butyl-2) -Methylcyclopentadienyl)
Vanadium trichloride, (1-methyl-2-bis (trimethylsilyl) methylcyclopentadienyl) vanadium trichloride, 1,2-bis (trimethylsilyl) cyclopentadienyl) vanadium trichloride, (1-methyl-2-phenyl) (Cyclopentadienyl) vanadium trichloride, (1-methyl-2-tolylcyclopentadienyl) vanadium trichloride, (1-methyl-2- (2,6-dimethylphenyl)
Cyclopentadienyl) vanadium trichloride.

(Ii) 1,3-disubstituted cyclopentadienyl vanadium trichloride such as (1,3
-Dimethylcyclopentadienyl) vanadium trichloride, (1-ethyl-3-methylcyclopentadienyl) vanadium trichloride, (1-methyl-3-propylcyclopentadienyl) vanadium trichloride, (1-butyl- 3-methylcyclopentadienyl)
Vanadium trichloride, (1-methyl-3-bis (trimethylsilyl) methylcyclopentadienyl) vanadium trichloride, 1,3-bis (trimethylsilyl) cyclopentadienyl) vanadium trichloride, (1-methyl-3-phenyl) (Cyclopentadienyl) vanadium trichloride, (1-methyl-3-tolylcyclopentadienyl) vanadium trichloride, (1-methyl-3- (2,6-dimethylphenyl)
Cyclopentadienyl) vanadium trichloride.

(Iii) 1,2,3-trisubstituted cyclopentadienyl vanadium trichloride, for example,
(1,2,3-trimethylcyclopentadienyl) vanadium trichloride and the like.

(Iv) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride, for example,
(1,2,4-trimethylcyclopentadienyl) vanadium trichloride and the like.

(V) Tetra-substituted cyclopentadienyl vanadium trichloride such as (1,2,3,4
-Tetramethylcyclopentadienyl) vanadium trichloride, (1,2,3,4-tetraphenylcyclopentadienyl) vanadium trichloride and the like.

(Vi) penta-substituted cyclopentadienyl vanadium trichloride, for example (pentamethylcyclopentadienyl) vanadium trichloride,
(1,2,3,4-tetramethyl-5-phenylcyclopentadienyl) vanadium trichloride, (1-methyl-2,3,4,5-tetraphenylcyclopentadienyl) vanadium trichloride and the like can be mentioned. Can be

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

(Ix) Monoalkoxides, dialkoxides, trialkoxides and the like in which the chlorine atom of the compounds (i) to (viii) is substituted with an alkoxy group. For example, cyclopentadienyl vanadium tri-t-
Butoxide, cyclopentadienyl vanadium i-propoxide, cyclopentadienyl vanadium dimethoxychloride, trimethylsilylcyclopentadienyl vanadium dii-propoxycyclolide, cyclopentadienyl vanadium dit-butoxycyclolide, cyclopentadienyl vanadium diphenoxycyclolide ,
Cyclopentadienyl vanadium i-propoxy dichloride, cyclopentadienyl vanadium t-butoxy dichloride, cyclopentadienyl vanadium phenoxy dichloride, trimethylsilylcyclopentadienyl vanadium tri-t-butoxide, trimethylcyclopentadienyl vanadium tri i-propoxide,
Trimethylsilylcyclopentadienyl vanadium dimethoxychloride, trimethylsilylcyclopentadienyl vanadium dii-propoxychloride, trimethylsilylcyclopentadienyl vanadium dit-butoxycyclolide, trimethylsilylcyclopentadienyl vanadium diphenoxycyclolide, trimethylsilylcyclopentadienyl vanadium i -Propoxydichloride, trimethylsilylcyclopentadienyl vanadium t-butoxydichloride, trimethylsilylcyclopentadienyl vanadium phenoxydichloride and the like.

(X) Methyl forms in which the chlorine atom in (i) to (ix) is substituted with a methyl group.

(Xi) R is bonded by a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethyl (eta ⁵ - cyclopentadienyl) silane vanadium dichloride, (t-butylamido) dimethyl (trimethyl- eta ⁵ - cyclopentadienyl) silane vanadium dichloride, (t-butylamido) dimethyl (tetramethyl Methyl-η ⁵ -cyclopentadienyl)
Silane vanadium dichloride and the like can be mentioned.

(Xii) A methyl compound in which the chlorine atom of (xi) is substituted with a methyl group.

(Xiii) Monoalkoxy and dialkoxy compounds in which the chlorine atom of (xi) is substituted with an alkoxy group.

(Xiv) Compounds obtained by substituting the monochloro compound of (xiii) with a methyl group.

(Xv) An amide in which the chlorine atom in (i) to (viii) is substituted with an amide group. For example, cyclopentadienyl tris (diethylamide) vanadium, silylcyclopentadienyl tris (i-propylamide) vanadium, cyclopentadienyl tris (n-octylamide) vanadium, cyclopentadienyl bis (diethylamide) vanadium chloride,
(Trimethylsilylcyclopentadienyl) bis (i-
(Propylamide) vanadium chloride, (trimethylsilylcyclopentadienyl) bis (n-octylamide) vanadium chloride, cyclopentadienyl (diethylamide) vanadium dichloride, cyclopentadienyl (i-propylamido) vanadium dichloride, cyclopentadienyl (N-octylamide) vanadium dichloride, (trimethylsilylcyclopentadienyl) tris (diethylamide) vanadium, (trimethylsilylcyclopentadienyl) tris (i-propylamido) vanadium, (trimethylsilylcyclopentadienyl) tris (n-octyl) Amido) vanadium, (trimethylsilylcyclopentadienyl) bis (diethylamido) vanadium chloride, (trimethylsilylcyclope Tajieniru) bis (i-propyl amide) vanadium chloride, (trimethylsilyl cyclopentadienyl) bis (n- octyl amide) vanadium chloride, (trimethylsilyl cyclopentadienyl) (diethylamide) vanadium dichloride,
(Trimethylsilylcyclopentadienyl) (i-propylamido) vanadium dichloride, (trimethylsilylcyclopentadienyl) (n-octylamido) vanadium dichloride, and the like.

(Xvi) A methyl compound in which the chlorine atom of (xv) is substituted with a methyl group.

Specific examples of the compound represented by RM (O) X ₂ include cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxovanadium dichloride, benzylcyclopentadienyloxovanadium dichloride, (1,3 -Dimethylcyclopentadienyl) oxovanadium dichloride, (1-
Butyl-3-methylcyclopentadienyl) oxovanadium dichloride, (pentamethylcyclopentadienyl) oxovanadium dichloride, (trimethylsilylcyclopentadienyl) oxovanadium dichloride, (1,3-bis (trimethylsilyl) cyclopentadienyl ) Oxovanadium dichloride, indenyloxovanadium dichloride, (2-methylindenyl) oxovanadium dichloride, (2-trimethylsilylindenyl) oxovanadium dichloride,
Fluorenyloxovanadium dichloride and the like. A methyl compound in which a chlorine atom of each of the above compounds is substituted with a methyl group is also included.

R and X include those linked by a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethyl (eta ⁵ - cyclopentadienyl) silane oxovanadium chloride, (t-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) amide such as silane oxovanadium chloride chloride thereof, Alternatively, a methyl compound in which a chlorine atom of these compounds is substituted with a methyl group may be used.

Cyclopentadienyloxovanadium dimethoxide, cyclopentadienyloxovanadium dii-propoxide, cyclopentadienyloxovanadium dit-butoxide, cyclopentadienyloxovanadium diphenoxide, cyclopentadienyloxo Vanadium methoxy chloride, cyclopentadienyl oxovanadium i-propoxycyclolide,
Examples thereof include cyclopentadienyloxovanadium t-butoxycyclolide and cyclopentadienyloxovanadium phenoxycyclolide. A methyl compound in which a chlorine atom of each of the above compounds is substituted with a methyl group is also included.

(Cyclopentadienyl) bis (diethylamide) oxovanadium, (cyclopentadienyl)
Bis (di-propylamido) oxovanadium, (cyclopentadienyl) bis (di-n-octylamido) oxovanadium and the like can be mentioned.

As the component (B) of the catalyst system of the present invention, at least one compound selected from the group consisting of an ionic compound of a coordinating anion and a cation, a Lewis acid compound, and an aluminoxane is used.

In the component (B), the non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation includes, for example, tetra (phenyl) borate and tetra (fluorophenyl) borate. , Tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl)
Borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate
, Tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tridecahydride-7,8-dicarboundecaborate, tetra Fluoroborate, 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.

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

Specific examples of the ammonium cation include:
Trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, N, N-dimethylanilinium cation;
N-diethylanilinium cation, N, N-2,4,
N, N- such as 6-pentamethylanilinium cation
Dialkylanilinium cation, di (i-propyl)
Examples thereof include a dialkylammonium cation such as an ammonium cation and a 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 from the non-coordinating anions and cations exemplified above and arbitrarily combined can be preferably used.

Among the ionic compounds, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) )
And 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate are preferred.

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

Examples of the Lewis acidic compound include fluorine compounds of boron or aluminum, tris (pentafluorophenyl) borane or aluminum, tris (tetrafluorophenyl) borane or aluminum, tris (trifluorophenyl) borane or aluminum, tris (difluoro Phenyl) borane or aluminum,
Tris (monofluorophenyl) borane, aluminum, triphenylborane, and the like can be given. The Lewis acidic compound can stabilize the cation of the transition metal compound by removing the ligand of the transition metal compound as an anion.

As the component (B), aluminoxane can be used. The aluminoxane 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 a degree of polymerization and is 5 or more;
Preferably it is 10 or more.) R 'is methyl,
Ethyl, propyl and isobutyl groups are mentioned, but methyl and ethyl groups are preferred. Examples of the organoaluminum compound used as a raw material of the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

Aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

Examples of the condensing agent include water, which is a typical one. In addition, any condensing agent capable of condensing the trialkylaluminum, such as water adsorbed on inorganic substances or diol, may be used. .

The conjugated diene may be polymerized by combining the components (A) and (B) with an organometallic compound of a Group 1 to 3 element of the periodic table as the component (C).
The addition of the component (C) has the effect of increasing the polymerization activity. Examples of the organometallic compounds of Group 1 to 3 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 and ethylaluminum dichloride, and hydrogenated organometallic compounds such as diethylaluminum hydride and sesquiethylaluminum hydride are also included. Two or more of the above-mentioned organometallic compounds can be used in combination.

The molar ratio of the components (A) and (B) is preferably from 1: 0.1 to 1:10, more preferably from 1: 0.1.
0.2 to 1: 5. When aluminoxane is used as the component (B), the molar ratio between the component (A) and the component (B) is preferably 1: 0.1 to 1: 10000, and more preferably 1: 0.2 to 1: 5000. It is.

The molar ratio of component (A) to component (C) is preferably from 1: 0.1 to 1: 1000, more preferably from 1:10 to 1: 1000, and still more preferably from 1:10 to 1: 1000.
1: 500.

The above components (A), (B) and (C)
Water may be further combined with the component as the component (D). The molar ratio of component (C) to water of component (D) (C) /
(D) is from 0.66 to 5, preferably from 0.7 to 5.
1.5, more preferably 0.8 to 1.5.

The order of addition of the catalyst component is not particularly limited, but can be, for example, in the following order. (I) The components (A) and (B) are added in any order to the conjugated diene compound monomer to be polymerized or a mixture of the monomer and the solvent. (Ii) After the component (C) is added to the conjugated diene compound monomer to be polymerized or a mixture of the monomer and the solvent, (A)
The components and component (B) are added in any order. (Iii) The component (D) is added to the conjugated diene compound monomer or the mixture of the monomer and the solvent to be polymerized, the component (C) is added, and then the components (A) and (B) are added in any order. Added. (Iv) The component (C) is added to the conjugated diene compound monomer to be polymerized or a mixture of the monomer and the solvent, the component (D) is added, and then the components (A) and (B) are added in any order. Added.

Here, the conjugated diene compound monomer to be polymerized may be a whole or a part. In the case of a part of the monomer, the above contact mixture is mixed with the remaining monomer.
Alternatively, it can be mixed with the remaining monomer solution.

The conjugated diene compound monomers include 1,1
3-butadiene, isoprene, 1,3-pentadiene,
Examples thereof include 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. These monomer components may be used in combination of two or more.

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 aromatic vinyl compounds such as styrene and α-methylstyrene, and non-conjugated diolefins such as 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. . Also, 1,3-butadiene itself may be used as the polymerization solvent.

Among them, toluene, cyclohexane, a mixture of cis-2-butene and trans-2-butene, and the like are preferably used.

In the present invention, using the above catalyst,
The molecular weight may be adjusted by polymerizing the conjugated diene compound in the presence of hydrogen.

The amount of hydrogen is preferably 500 mmol or less per 1 mol of the conjugated diene, or 20 ° C.
The pressure is 12 L or less at 1 atm, more preferably 50 mmol or less, or 1.2 L or less at 20 ° C. at 1 atm, still more preferably 0.005 to 20 mmol, or 0.00001 to 20 at 1 atm. 0.48 L. Further, hydrogen may be continuously introduced into the polymerization tank.

The polymerization temperature is preferably in the range of -100 to 120 ° C, particularly preferably in the range of -50 to 100 ° C. The polymerization time is preferably in the range of 10 minutes to 12 hours, and 30 minutes to 6 hours.
Time is particularly preferred.

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.

The polybutadiene obtained in the present invention comprises 1,
2-structure content is 4-30%, preferably 5-25%,
More preferably, the content of cis-1,4-structure is 65-95%, preferably 70-95%, more preferably 70-92%, and the content of trans-1,4-structure is 5-5%.
% Or less, preferably 4.5% or less, particularly preferably 0.1% or less.
5-4%.

If the microstructure is out of the above range, the reactivity of the polymer (such as graft reaction and cross-linking reactivity) is not appropriate, and the rubber-like properties when used as an additive or the like are deteriorated. It unfavorably affects the balance and appearance.

Further, by using the polymerization method of the present invention, the intrinsic viscosity [η] measured in toluene at 30 ° C.
Polybutadiene having a ratio of 0.1 to 20 can be produced. Further, by using the polymerization method of the present invention, polybutadiene having a weight average molecular weight of 10,000 to 4,000,000 determined by GPC using polystyrene as a standard substance can be produced.

These polybutadienes can be suitably used as impact modifiers for polystyrene.

[0076]

EXAMPLES 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. Microstructure was performed by infrared absorption spectroscopy. Cis 740 cm-1, transformer 980 cm-1, vinyl 9
The microstructure was calculated from the absorption intensity ratio of 10 cm-1.

(Example 1) [Preparation of pentavalent vanadium compound] Cyclopentadienyl vanadium oxydichloride (CpVOCl ₂ )
Chem. Ber. 93, 701 (1960). That is, cyclopentadienyl vanadium trichloride (CpVCl ₃ ) was reacted with oxygen and then recrystallized to obtain dark blue crystals. Elemental analysis values were consistent with the calculated values. This crystal 20.
2 mmol / l by dissolving 3 mg in toluene
A 50 ml solution of was prepared.

(Example 2) [Preparation of tetravalent vanadium compound] Cyclopentadienyl vanadium trichloride (CpVCl ₃ ) An
org. Allg. Chem. 423, 231 (197
It was synthesized by the method described in 6). That is, biscyclopentadienyl vanadium dichloride was reacted with thionyl chloride and then recrystallized to obtain black purple crystals. Elemental analysis values were consistent with the calculated values. By dissolving 22.2 mg of these crystals in toluene, 2 mmol
50 ml of a 1 / l solution were prepared.

(Example 3) [1,3-Butadiene polymerization] Absorbance Abs (5) at 511.5 nm of the solution prepared in Example 1 and 600 n
Abs (5) / A ratio with absorbance Abs (6) at m
bs (6) was found to be 0.75 by an absorptiometer.
Nine. 1,3-butadiene in toluene solution 194
2 ml of a 0.1 mol / l toluene solution of triethylaluminum per ml (containing 21.6 g of 1,3-butadiene)
(0.2 mmol) is added and the solution is kept at 30 ° C. [Ph ₃ CB
3 ml (3 μmol) of a 1 mmol / l toluene solution of (C ₆ F ₅ ) ₄ ] was added, and 1 ml (2 μmol) of the solution prepared in Example 1 was added to carry out polymerization for 5 minutes. The polymerization was stopped with an antioxidant-containing ethanol solution, filtered and dried to obtain 3.25 g of a white butadiene polymer. Microstructure is cis 88.7
%, Trans 1.7% and vinyl 9.6%. Further, the weight average molecular weight was 2440000, and Mw / Mn was 2.52.

(Example 4) [1,3-Butadiene polymerization] Absorbance at 511.5 nm of a solution obtained by mixing 7.5 mL of the solution prepared in Example 1 and 2.5 mL of the solution prepared in Example 2 Ab
The ratio Abs (5) / Abs (6) between s (5) and the absorbance Abs (6) at 600 nm was 0.944 as determined by an absorptiometer. 1 ml of this solution (2μ
mol) was added in place of 1 mL of the solution prepared in Example 1, and polymerization was carried out in the same manner as in Example 3. 4.42 g of a white butadiene polymer was obtained. The microstructure was cis 88.4%, trans 1.9%, vinyl 9.7%. The weight average molecular weight was 2530000, Mw
/ Mn was 2.41.

(Example 5) [1,3-Butadiene polymerization] Absorbance at 511.5 nm of a solution obtained by mixing 5.0 ml of the solution prepared in Example 1 and 5.0 ml of the solution prepared in Example 2 Ab
The ratio Abs (5) / Abs (6) between s (5) and absorbance Abs (6) at 600 nm was determined by an absorptiometer to be 1.167. 1.0 ml of this solution
(2 μmol) was polymerized in the same manner as in Example 3 except that 1.0 ml of the solution prepared in Example 1 was added. 5.73 g of a white butadiene polymer was obtained. The microstructure was cis 88.5%, trans 2.0%, vinyl 9.5%. The weight average molecular weight is 24700
00, Mw / Mn was 2.32.

(Example 6) [1,3-Butadiene polymerization] Absorbance at 511.5 nm of a solution obtained by mixing 7.5 ml of the solution prepared in Example 1 and 2.5 ml of the solution prepared in Example 2 Ab
The ratio Abs (5) / Abs (6) between s (5) and the absorbance Abs (6) at 600 nm was determined by an absorptiometer to be 1.439. 1.0 ml of this solution
(2 μmol) was polymerized in the same manner as in Example 3 except that 1.0 mL of the solution prepared in Example 1 was added. 8.17 g of a white butadiene polymer was obtained. The microstructure was cis 88.4%, trans 2.1%, vinyl 9.5%. The weight average molecular weight is 25400
00, Mw / Mn was 2.38.

(Example 7) [1,3-Butadiene polymerization] Absorbance Abs (5) at 511.5 nm of the solution prepared in Example 2 and 600 n
Abs (5) / A ratio with absorbance Abs (6) at m
When bs (6) was determined with an absorptiometer, it was 1.77.
It was 8. Polymerization was carried out in the same manner as in Example 3 except that 1.0 ml (2 μmol) of this solution was added instead of 1.0 ml of the solution prepared in Example 1. 10.47 g of a white butadiene polymer was obtained. Microstructure is cis 8
8.4%, trans 1.9%, and vinyl 9.7%. The weight average molecular weight was 2620000, Mw / M
n was 2.33.

(Example 8) [1,3-Butadiene polymerization] 194 ml (1,3) of a 1,3-butadiene toluene solution passed through a molecular sieve
21.6 g of butadiene), add 2 μl of water,
Stir and dissolve. The water content of this solution was measured with a Karl Fischer moisture meter, and was found to be an average of 14 ppm (the total water content of the solution was 2.7 mg, 150 μmol). 194 ml of a toluene solution of 1,3-butadiene (21.6 in 1,3-butadiene) obtained by the same operation except that the water content was not measured.
g), 0.1 mol / l of triethylaluminum
2 ml (0.2 mmol) of a toluene solution are added and the solution is
Keep at 0 ° C. (Al / water = 1.3, but molar ratio). [Ph ₃ CB
3 ml (3 μmol) of a 1 mmol / l toluene solution of (C ₆ F ₅ ) ₄ ] was added, and 1 ml (2 μmol) of the solution prepared in Example 5 was added to carry out polymerization for 5 minutes. The polymerization was stopped with an ethanol solution containing an antioxidant, filtered and dried to obtain 6.56 g of a white butadiene polymer. Microstructure is cis 88.5
%, Trans 1.8%, and vinyl 9.7%. Further, the weight average molecular weight was 2550000, and Mw / Mn was 2.51.

Comparative Example 1 [1,3-Butadiene Polymerization] Polymerization was carried out in the same manner as in Example 8 except that the amount of water was changed to 6 μl (Al / water = 0.5).
4. However, the white butadiene polymer was 0.1 mol.
51 g were obtained. The microstructure was cis 87.9%, trans 2.3%, vinyl 9.8%. Further, the weight average molecular weight was 1980000, and Mw / Mn was 2.60.

Comparative Example 2 [1,3-Butadiene Polymerization] Polymerization was carried out in the same manner as in Example 8 except that the amount of triethylaluminum was changed to 1 mmol (Al / water = 6.6, but in a molar ratio). However, 1.82 g of a white butadiene polymer was obtained. Microstructure is cis 8
8.1%, trans 2.0%, and vinyl 9.9%. Also, the weight average molecular weight is 213,000, Mw / M
n was 2.54.

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Claims (5)

[Claims] 1. A mixture of vanadium complexes, wherein the toluene solution has a maximum absorbance Abs at 450 to 549 nm.
(5) and the maximum absorbance Abs at 550 to 650 nm
The ratio Abs (5) / Abs (6) to (6) is 0.7 to
1.8. A vanadium complex composition, wherein the composition is 1.8. 2. The mixture of the vanadium complex is composed of RMX ₃ and a general formula RM (O) X _{2 wherein} M represents a vanadium metal and R represents a cyclopentadienyl group or a substituted cyclopentadienyl group. , X represents a halogen.), A vanadium complex composition. 3. A compound selected from the group consisting of (A) the vanadium complex composition according to claim 1 or 2, and (B) an ionic compound of a non-coordinating anion and a cation, a Lewis acid compound, and aluminoxane. A catalyst obtained from at least one compound obtained. 4. The vanadium complex composition according to claim 1, wherein (A) an ionic compound of a non-coordinating anion and a cation, and (C) a group 1 to 3 group of the periodic table. Elemental organometallic compound and (D) water (provided that (C) /
(D) = 0.66 to 5 (molar ratio). The catalyst obtained from 5. A method for producing a conjugated diene polymer, comprising using the catalyst according to claim 3 or 4.