JP2000017008A - Production of conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing conjugated diene polymer having a regulated microstructure in a catalytic system using a metallocene type complex of a group V transition metal compound in the periodic table with a high polymerization activity. SOLUTION: Bulk polymerization is carried out in the polymerization of a conjugated diene compound with use of a catalyst obtained from (A) a metallocene type complex of a group V transition metal compound, (B) an ionic compound of non-coordinated anion and cation, (C) an organoaluminum compound and (D) water or a catalyst consisting of (A) a metallocene type complex of a group V transition metal compound in the periodic table, (B) an ionic compound of a non-coordinated anion and cation, (C) an organo- aluminum compound, and (D) water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conjugated dienes are known to yield polymers having various microstructures by a polymerization catalyst. A method for producing a polybutadiene having a high cis structure using a cobalt compound and an organoaluminum compound is known.However, a polybutadiene containing a 1,2-structure in a high cis structure appropriately imparts impact resistance to a vinyl aromatic polymer. Agents are expected.

In recent years, the development of various olefin polymerizations using a metallocene-based complex as a catalyst has been actively promoted, and studies have been made on the polymerization of conjugated dienes.

As the polymerization of a conjugated diene using a metallocene type complex, for example, Macromol. Symp., 89, 383
(1995) states that cyclopentadienyltitanium trichloride (CpTiC
Although a catalyst system comprising l ₃ ) and methylalumoxane has been reported, it has a problem of low polymerization activity.

Japanese Patent Publication No. 46-20494 discloses CpVCl _3.
+ But _{(i-C 4 H 9)} 3 Al / AlCl 3 + H method for producing a polybutadiene according catalyst system comprising ₂ O is disclosed, the polymerization activity is low problem.

Further, Polymer vol. 37 (2) p. 363 (19
96) describes vanadium (III) such as Cp'VCl ₂ or Cp ₂ VCl, which is a metallocene complex of a transition metal of Group 5 of the periodic table.
Using a catalyst consisting of the compound and methylalumoxane,
A method for producing a polybutadiene containing 10 to 20% of a 1,2-structure in a high cis structure has been reported.

Further, JP-A-9-20813 and JP-A-9-194526 disclose a method for producing polybutadiene in a catalyst system comprising a vanadium metallocene compound having a specific structure and an ionizing agent.

[0008]

SUMMARY OF THE INVENTION The present invention provides a method for producing a conjugated diene polymer having a controlled microstructure with high polymerization activity in a catalyst system using a metallocene complex of a transition metal compound of Group V of the periodic table. The purpose is to:

[0009]

The present invention provides (A) a metallocene complex of a transition metal compound of Group V of the periodic table, (B) an ionic compound of a non-coordinating anion and a cation, (C)
In a method for polymerizing a conjugated diene compound using a catalyst obtained from an organoaluminum compound and (D) water, a method for producing a conjugated diene polymer, wherein the component (C) and the component (D) are brought into contact in advance. About.

Further, the present invention provides (A) a metallocene complex of a transition metal compound of Group V of the periodic table, (B) an ionic compound of a non-coordinating anion and a cation, (C) an organoaluminum compound, and D) A method for polymerizing a conjugated diene compound using a catalyst comprising water, which relates to a method for producing a conjugated diene polymer, wherein the component (C) and the component (D) are brought into contact in advance.

[0011]

The metallocene complex of the embodiment of the Invention (A) the periodic table group 5 transition metal _{compound, (1) RMX 3 · L} a (2) R n MX 3-n · L a (3) RM (O) X ₂ · L _a (4) R _n MX _3-n (NR ′) (5) Transition of group 5 of the Periodic Table having at least one ligand of cycloalkadienyl group and oxidation number + 2 Metal compound (6) A compound represented by a general formula such as a transition metal compound belonging to Group 5 of the periodic table having an oxidation number of +1 and having a ligand of a cycloalkadienyl group. In the above formula, n is 1-2 and a is 0, 1 or 2.

M represents a transition metal compound of Group 5 of the periodic table. Specifically, it is vanadium (V), niobium (Nb), or tantalum (Ta), and a preferable metal is 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, t-butyl, hexyl And the like, a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, an aromatic hydrocarbon group such as phenyl, tolyl, naphthyl and benzyl, and a silicon-containing hydrocarbon group such as trimethylsilyl. Further, those in which a cyclopentadienyl ring is bonded to a part of X by a crosslinking 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, 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. 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.

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 linear groups such as methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, t-butyl and hexyl. Examples thereof include an aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, 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 represents a fluorine atom,
Preferred are a chlorine atom, a bromine atom, methyl, ethyl, butyl, 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 a metal with a counter electron. Among them, compounds having no active hydrogen are particularly preferred. Specific examples include ethers, esters, ketones, amines, phosphines, and silyloxy compounds.

NR 'is an imide group, and R' is a hydrocarbon substituent having 1 to 25 carbon atoms. Specific examples of R ′ include:
Straight-chain or branched aliphatic hydrocarbon groups such as methyl, ethyl, propyl, iso-propyl, sec-butyl, t-butyl, hexyl, octyl, neopentyl, phenyl, tolyl, naphthyl, benzyl, Examples include aromatic hydrocarbon groups such as methylphenylmethyl, dimethylphenyl, 2,6-dimethylphenyl, and 3,4-dimethylphenyl. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included.

(A) Examples of the metallocene complex of a transition metal compound belonging to Group 5 of the periodic table include RMX ₃ , RM (O) X ₂ ,
R ₂ MX · L _a, such as the RMX ₂ · L _a is preferable. Among them, RVX ₃ , RV (O) X ₂ , wherein M is vanadium,
R ₂ VX · L _a, vanadium compounds such as RVX ₂ · L _a is preferable.

[0026] As specific compounds represented by RMX ₃ include the following of (i) ~ (xvi).

(I) Cyclopentadienyl vanadium trichloride. Mono-substituted cyclopentadienyl vanadium trichloride, for example, methylcyclopentadienyl vanadium trichloride, ethyl cyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, isopropylcyclopentadienyl vanadium trichloride, t- Butylcyclopentadienyl vanadium trichloride, (1,1-dimethylpropyl) cyclopentadienyl vanadium trichloride, (1,1-dimethylbenzyl) cyclopentadienyl vanadium trichloride,
(1-ethylpropyl) cyclopentadienyl vanadium trichloride, (1-ethyl, 1-methylpropyl) cyclopentadienyl vanadium trichloride, (diethylbenzyl) cyclopentadienyl vanadium trichloride, (trimethylsilylcyclopentadienyl ) Vanadium trichloride, (bis (trimethylsilyl)
(Cyclopentadienyl) vanadium trichloride and the like.

(Ii) 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-phenyl) (Cyclopentadienyl) 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.

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

(Iv) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride, such as (1,2,4-trimethylcyclopentadienyl) vanadium trichloride.

(V) tetra-substituted cyclopentadienyl vanadium trichloride, for example, (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, (1,2,3,4-tetraphenyl
-5-methylcyclopentadienyl) vanadium trichloride.

(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,
Trimethylsilylcyclopentadienyl vanadium tri
ter-butoxide, trimethylcyclopentadienyl vanadium tri-iso-propoxide, trimethylsilylcyclopentadienyl vanadium dimethoxy chloride,
Trimethylsilylcyclopentadienyl vanadium diis
o-propoxycyclolide, trimethylsilylcyclopentadienyl vanadium diter-butoxycyclolide, trimethylsilylcyclopentadienyl vanadium diphenoxycyclolide, trimethylsilylcyclopentadienyl vanadium iso-propoxydichloride, trimethylsilylcyclopentadienyl vanadium ter-butoxydichloride, trimethylsilyl Cyclopentadienyl vanadium phenoxy dichloride,

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

(Xi) those wherein 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) silanevanadium dichloride.

(Xii) A dimethyl form 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 by an amide group. For example, (trimethylsilylcyclopentadienyl) (trisdiethylamido) vanadium, (trimethylsilylcyclopentadienyl) (trisiso-propylamido) vanadium,
(Trimethylsilylcyclopentadienyl) (tris n-
(Octylamide) vanadium, (trimethylsilylcyclopentadienyl) (bisdiethylamide) vanadium chloride, (trimethylsilylcyclopentadienyl) (bisiso-propylamido) vanadium chloride, (trimethylsilylcyclopentadienyl) (bis
(n-octylamide) vanadium chloride, (trimethylsilylcyclopentadienyl) (diethylamide) vanadium dichloride, (trimethylsilylcyclopentadienyl) (iso-propylamido) vanadium dichloride, (trimethylsilylcyclopentadienyl)
(N-octylamide) vanadium dichloride and the like.

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

[0042] Among the specific compounds represented by _{R n MX 3-n · L} a, as the compound n = 1, the cyclopentadienyl vanadium dichloride, methylcyclopentadienyl vanadium dichloride, (1,3 -Dimethylcyclopentadienyl) vanadium dichloride, (1-methyl
-3-butylcyclopentadienyl) vanadium dichloride, (pentamethylcyclopentadienyl) vanadium dichloride, (trimethylsilylcyclopentadienyl) vanadium dichloride, (1,3-di (trimethylsilyl) cyclopentadienyl) vanadium dichloride, Dichlorides such as indenyl vanadium dichloride, (2-methylindenyl) vanadium dichloride, (2-trimethylsilylindenyl) vanadium dichloride, and fluorenyl vanadium dichloride, or dimethyl compounds in which the chlorine atom of these compounds is substituted with a methyl group And the like.

R and X include those linked by a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethylsilyl (eta ⁵ - cyclopentadienyl) vanadium dichloride, (t-butylamido) dimethylsilyl (tetramethyl-eta ⁵ - cyclopentadienyl) vanadium chloride amide chloride of such ride, or they Amides obtained by substituting a chlorine atom with a methyl group of the compound of the formula (1).

Cyclopentadienyl vanadium dimethoxide, cyclopentadienyl vanadium diiso-propoxide, cyclopentadienyl vanadium diter-butoxide, cyclopentadienyl vanadium diphenoxide, cyclopentadienyl vanadium methoxy chloride, cyclopentadienyl vanadium diphenoxide Alkoxides such as pentadienyl vanadium iso-propoxychloride, cyclopentadienyl vanadium ter-butoxycyclolide, cyclopentadienyl vanadium phenoxycyclolide, and methyl compounds in which chlorine atoms of these compounds are substituted with a methyl group. .

Bisamides such as (cyclopentadienyl) (bisdiethylamido) vanadium, (cyclopentadienyl) (bisdiiso-propylamido) vanadium, (cyclopentadienyl) (bisdi-n-octylamido) vanadium and the like can be mentioned. Can be

Cyclopentadienyl vanadium dichloride / bistriethylphosphine complex, cyclopentadienyl vanadium dichloride / bistrimethylphosphine complex, (cyclopentadienyl) (bisdiiso-propylamido) vanadium trimethylphosphine complex, monomethylcyclopentadienyl And phosphine complexes such as vanadium dichloride bistriethylphosphine complex.

[0047] Among the specific compounds represented by _{R n MX 3-n · L} a, as the compound n = 2, the dicyclopentadienyl vanadium dichloride, bis (methylcyclopentadienyl) vanadium chloride, Bis (1,3-dimethylcyclopentadienyl) vanadium chloride, bis (1-methyl-3-butylcyclopentadienyl) vanadium chloride, bis (pentamethylcyclopentadienyl) vanadium chloride, bis (trimethylsilylcyclopentadiene) Enyl) vanadium chloride, bis (1,3-di (trimethylsilyl) cyclopentadienyl)
Chloride such as vanadium chloride, diindenyl vanadium chloride, bis (2-methylindenyl) vanadium chloride, bis (2-trimethylsilylindenyl) vanadium chloride, difluorenyl vanadium chloride, or the chlorine atom of these compounds is converted to methyl. And methyl groups substituted with a group.

Dicyclopentadienyl vanadium methoxide, dicyclopentadienyl vanadium iso-propoxide, dicyclopentadienyl vanadium ter-butoxide, dicyclopentadienyl vanadium phenoxide, dicyclopentadienyl diethylamide vanadium, Cyclopentadienyl di-iso-propylamido vanadium and dicyclopentadienyl di-n-octylamido vanadium.

The compounds in which R is bonded by a hydrocarbon group or a silyl group are also included. For example, dimethyl bis (eta ⁵ - cyclopentadienyl) silane vanadium chloride, dimethyl bis (tetramethyl-eta ⁵ - cyclopentadienyl) silane vanadium chloride chlorides body such as,
Alternatively, a methyl compound in which a chlorine atom of these compounds is substituted with a methyl group may be used.

Specific examples of the compound represented by RM (O) X ₂ 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) oxovanadium dichloride, indenyloxovanadium dichloride, (2-methylindenyl) oxovanadium dichloride, (2-trimethylsilylindenyl) oxovanadium dichloride, Fluorenyloxovanadium dichloride and the like. A dimethyl form in which a chlorine atom of each of the above compounds is substituted with a methyl group is also included.

[0051] Also included are those in which R and X are 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, amides obtained by substituting a chlorine atom of these compounds with a methyl group may be mentioned.

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

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

Specific examples of the compound represented by R _n MX _3-n (NR ′) include cyclopentadienyl (methylimido) vanadium dichloride, cyclopentadienyl (phenylimido) vanadium dichloride, cyclopentadienyl ( 2,6-dimethylphenylimide) vanadium dichloride, cyclopentadienyl (2,6-diiso-propylphenylimide) vanadium dichloride, (methylcyclopentadienyl) (phenylimide) vanadium dichloride, (1,3-dimethyl Cyclopentadienyl) (phenylimide) vanadium dichloride, (1-
Methyl-3-butylcyclopentadienyl) (phenylimide) vanadium dichloride, (pentamethylcyclopentadienyl) (phenylimide) vanadium dichloride, indenyl (phenylimide) vanadium dichloride, 2-methylindenyl (phenylimide) vanadium Dichloride, fluorenyl (phenylimide)
And dichlorides such as vanadium dichloride.

[0055] R and X include those bonded by a hydrocarbon group or a silyl group. For example, (t-butylamide)
Dimethyl (eta ⁵ - cyclopentadienyl) silane (phenyl imide) vanadium chloride, (t-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane (phenyl imide) amide chloride of vanadium chloride, or An amide in which a chlorine atom of these compounds is substituted with a methyl group is exemplified.

The compounds in which R is bonded by a hydrocarbon group or a silyl group are also included. For example, dimethyl bis (eta ⁵ - cyclopentadienyl) silane (phenyl imide) vanadium dichloride, dimethyl bis (eta ⁵ - cyclopentadienyl) silane (Toriruimido) vanadium chloride, dimethyl (tetramethyl- eta ⁵ - Shikuropentaji enyl) silane (phenyl imide) vanadium chloride, dimethyl (tetramethyl- eta ⁵ - cyclopentadienyl) silane (Toriruimido) amide chloride of vanadium chloride, or amide obtained by substituting chlorine atoms of these compounds with a methyl group And the like.

Cyclopentadienyl vanadium (phenylimide) dimethoxide, cyclopentadienyl vanadium (phenylimide) diiso-propoxide, cyclopentadienyl vanadium (phenylimide) (iso-
(Propoxy) chloride, (cyclopentadienyl)
(Bisdiethylamide) vanadium (phenylimide), (cyclopentadienyl) (bisiso-propylamide) vanadium (phenylimide) and the like.

When the transition metal of Group 5 of the Periodic Table having an oxidation number of +2 having at least one ligand of a cycloalkadienyl group has two cycloalkadienyl groups as ligands, Each cycloalkadienyl ring is a Me ₂ Si group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group,
Also included are those linked by a cross-linking group such as a substituted ethylene group.

When the compound has one cycloalkadienyl group as a ligand, the other sigma-binding ligand may be a halogen atom such as hydrogen, chlorine, bromine or iodine, a methyl group,
Hydrocarbon groups such as phenyl group, benzyl group, neopentyl group, trimethylsilyl group and bistrimethylsilylmethyl group, hydrocarbon oxy groups such as methoxy group, ethoxy group and isopropoxy group, dimethylamino group, diethylamino group, diisopropylamino group, dioctyl It can have a hydrocarbon amino group such as an amino group.

Further, as another ligand, a neutral Lewis base such as amine, amide, phosphine, ether, ketone and ester can be used. Lewis bases without active hydrogen are preferred.

Specific examples of the transition metal compound belonging to Group 5 of the Periodic Table having an oxidation number of +2 and having one cycloalkadienyl group as a ligand according to the present invention include chlorocyclopentadienyl (tetrahydrofuran) vanadium and chlorocyclopentane. Dienyl (trimethylphosphine) vanadium, chlorocyclopentadienyl bis (trimethylphosphine)
Vanadium, chlorocyclopentadienyl (1,2-bisdimethylphosphinoethane) vanadium, chlorocyclopentadienyl (1,2-bisdiphenylphosphinoethane) vanadium, chlorocyclopentadienyl (triphenylphosphine) vanadium, Chlorocyclopentadienyl (tetrahydrothiophene) vanadium, bromocyclopentadienyl (tetrahydrofuran) vanadium, iodocyclopentadienyl (tetrahydrofuran) vanadium, chloro (methylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (1,
3-dimethylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (1-methyl-3-butylcyclopetadienyl) (tetrahydrofuran) vanadium,
Chloro (tetramethylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (pentamethylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (trimethylsilylcyclopentadienyl)
(Tetrahydrofuran) vanadium, chloro (1,2-bis (trimethylsilyl) cyclopentadienyl) (tetrahydrofuran) vanadium, chloro (1,3-bis (trimethylsilyl) cyclopentadienyl) (tetrahydrofuran) vanadium, chloroindenyl (tetrahydrofuran) ) Vanadium, chloro (2-methylindenyl) (tetrahydrofuran) vanadium, chloro (2-
Trimethylsilylindenyl) (tetrahydrofuran)
Vanadium, chlorofluorenyl (tetrahydrofuran) vanadium, dimethylsilyl (cyclopentadienyl) (t-butylamino) vanadium, dimethylsilyl (pentamethylcyclopentadienyl) (t-butylamino) vanadium and the like can be mentioned.

Specific examples of the transition metal compound of Group 5 of the Periodic Table having two oxidations having two cycloalkadienyl groups as ligands of the present invention include biscyclopentadienyl vanadium and bis (methylcyclopentane). Dienyl) vanadium, bis (1,2-dimethylcyclopentadienyl) vanadium, bis (1,3-dimethylcyclopentadienyl) vanadium, bis (1-methyl-3-butylcyclopetadienyl) vanadium, bis (Tetramethylcyclopentadienyl) vanadium, bis (pentamethylcyclopentadienyl) vanadium, bis (ethylcyclopentadienyl) vanadium, bis (n-propylcyclopentadienyl) vanadium, bis (i-propylcyclopenta Dienyl) vanadium, bis (n-butylcyclopentadienyl) vanadium , Bis (i-butylcyclopentadienyl) vanadium, bis (sec-butylcyclopentadienyl) vanadium, bis (t-butylcyclopentadienyl) vanadium, bis (1-methoxyethylcyclopentadienyl) vanadium , Screws (1-
Dimethylaminoethylcyclopentadienyl) vanadium, bis (1-diethylaminoethylcyclopentadienyl) vanadium, bis (trimethylsilylcyclopentadienyl) vanadium, bis (1-dimethylphosphinoethylcyclopentadienyl) vanadium, bis ( 1,2-bis (trimethylsilyl) cyclopentadienyl) vanadium, bis (1,3-bis (trimethylsilyl) cyclopentadienyl) vanadium, indenylcyclopentadienyl vanadium, (2-methylindenyl) cyclopentadi Enyl vanadium, (2-trimethylsilylindenyl) cyclopentadienyl vanadium, bisindenyl vanadium, bisfluorenyl vanadium, indenyl fluorenyl vanadium, cyclopentadienyl fluorenyl vana Dimethylsilyl (cyclopentadienyl) (t-butylamino) vanadium, dimethylsilyl (pentamethylcyclopentadienyl) (t-butylamino) vanadium, dimethylsilylbis (cyclopentadienyl) vanadium, dimethylsilylbis (Indenyl) vanadium, dimethylsilylbis (fluorenyl) vanadium and the like can be mentioned.

Examples of the transition metal compound belonging to Group 5 of the Periodic Table having an oxidation number of +1 and having a ligand of a cycloalkadienyl group include:
Cyclopentadienyl (benzene) vanadium, cyclopentadienyl (toluene) vanadium, cyclopentadienyl (xylene) vanadium, cyclopentadienyl (trimethylbenzene) vanadium, cyclopentadienyl (hexamethylbenzene) vanadium, cyclopenta Dienyl (naphthalene) vanadium, cyclopentadienyl (anthracene) vanadium, cyclopentadienyl (ferrocene) vanadium, methylcyclopentadienyl (benzene) vanadium, 1,3-dimethylcyclopentadienyl (benzene) vanadium, 1 -Methyl-3-
Butylcyclopetadienyl (benzene) vanadium, tetramethylcyclopentadienyl (benzene) vanadium, pentamethylcyclopentadienyl (benzene) vanadium, trimethylsilylcyclopentadienyl (benzene) vanadium, 1,2-bis (trimethylsilyl) Cyclopentadienyl (benzene) vanadium, 1,3-bis (trimethylsilyl) cyclopentadienyl (benzene) vanadium, indenyl (benzene) vanadium,
2-methylindenyl (benzene) vanadium, 2-trimethylsilylindenyl (benzene) vanadium, fluorenyl (benzene) vanadium, cyclopentadienyl (ethylene) (trimethylphosphine) vanadium, cyclopentadienyl (butadiene) (trimethylphosphine) Vanadium, cyclopentadienyl (1,4-diphenylbutadiene) (trimethylphosphine) vanadium, cyclopentadienyl (1,1,4,4-tetraphenylbutadiene) (trimethylphosphine) vanadium, cyclopentadienyl (2, 3-dimethylbutadiene) (trimethylphosphine) vanadium, cyclopentadienyl (2,4-hexadiene) (trimethylphosphine) vanadium, cyclopentadienyltetracarbonylvanadium And indenyl tetracarbonyl vanadium.

In the component (B) of the present invention, examples of the non-coordinating anion constituting the ionic compound of a non-coordinating anion and a cation include tetra (phenyl) borate and tetra (fluorophenyl) borate. , Tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (3,5-bistrifluoromethyl) Phenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, (triphenyl,
(Pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate, tetrafluoroborate, hexafluorophosphate and the like.

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:
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 -
Examples thereof include N, N-dialkylanilinium cations such as pentamethylanilinium cation, dialkylammonium cations such as di (i-propyl) ammonium cation and 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.

As the ionic compound, a non-coordinating anion and a cation arbitrarily selected and combined can be preferably used.

Among them, ionic compounds include triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferred.

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

Specific examples of the organoaluminum compound (C) of the present invention include trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, and the like.
Organic aluminum halides such as sesquiethylaluminum chloride and ethylaluminum dichloride, and organic aluminum hydride compounds such as diethylaluminum hydride and sesquiethylaluminum hydride are exemplified. The above organoaluminum compounds can be used in combination of two or more.

The molar ratio of the metallocene complex of component (A) to the ionic compound of component (B) is preferably 1: 0.1
To 1:10, more preferably 1: 0.2 to 1: 5.

The molar ratio of the metallocene complex of the component (A) to the organoaluminum compound of the component (C) is preferably
1: 0.1 to 1: 1000, more preferably 1: 0.2 to
1: 500.

The molar ratio (C) :( D) of the organoaluminum compound of component (C) to water of component (D) is preferably from 1: 0.1 to 2, and particularly preferably from 1: 0. Two
1.5.

The order of addition of the catalyst components is preferably such that the organoaluminum compound of component (C) and the water of component (D) are brought into contact in advance. For example, it can be performed in the following order.

After the component (D) is added to the conjugated diene compound monomer to be polymerized, and the component (C) is added, the component (A)
The components and component (B) are added in any order. After the component (C) is added to the conjugated diene compound monomer to be polymerized and the component (D) is added, the components (A) and (B) are added.
The components are added in any order.

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

The conjugated diene compound monomers include 1,3-
Butadiene, isoprene, 1,3-pentadiene, 2-ethyl
Examples thereof include -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, ethylene, propylene, butene-1, butene-2, isobutene, pentene-
Acyclic monoolefins such as 1,4-methylpentene-1, hexene-1, and octene-1, cyclopentene, cyclohexene, and cyclic monoolefins such as norbornene, and / or aromatic vinyl compounds such as styrene and α-methylstyrene; Non-conjugated diolefins such as dicyclopentadiene, 5-ethylidene-2-norbornene and 1,5-hexadiene may be contained in small amounts.

In the present invention, the polymerization method is a bulk polymerization (bulk polymerization), that is, a bulk polymerization using a conjugated diene itself as a polymerization solvent. Bulk polymerization has the advantage that it does not require much energy for solvent recovery.

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 50 mmol or less per 1 mol of the conjugated diene, or 20 ° C.
It is 1.2L or less at 1 atm, more preferably 0.005 ~
20 mmol, or 0.001 to 0.48 L at 20 ° C and 1 atmosphere
It is. Further, hydrogen may be continuously introduced into the polymerization tank.

[0084] 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 has been 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.

By using the polymerization method of the present invention, the 1,2-structure content is 4 to 30%, preferably 5 to 25%.
%, More preferably 5 to 20%, cis-1,4-structure content of 65 to 95%, preferably 70 to 95%, trans-1,4-structure content of 5% or less, preferably 4.5% The following polybutadiene can be produced.

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

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

[0089]

EXAMPLES The microstructure of polybutadiene was determined by infrared absorption spectroscopy. Cis-1,4-structure 740cm
^The microstructure was calculated from the absorption intensity ratio of ^-1 , trans-1,4-structure of 967 cm ^-1 and 1,2-structure (vinyl) of 911 cm ^-1 .

[Η] of polybutadiene was measured at 30 ° C. in a toluene solution.

First, the amount of water present in a 1.5-liter autoclave system (hereinafter referred to as base water content) was measured according to the following procedure. [Operation Details] The inside of a 1.5 L autoclave was replaced with nitrogen, and 1.0 L of 1,3-butadiene was charged through molecular sieves and stirred. Next, water shown in Table 1 was added, and dissolved by stirring for 30 minutes. The water content was measured with a Karl Fischer moisture meter, and the value of water content in butadiene shown in Table 1 was obtained. The same operation was performed a total of five times while changing the level of the added water. The base water content was calculated from the average of five times the difference between the water content in butadiene and the added water content. As a result, a value of 4 mg was obtained. Thereafter, the value of TEA / H ₂ O was calculated in consideration of this value.

(Examples 1 to 5) The interior of an autoclave having a content of 1.5 L was replaced with nitrogen, and 1.0 L of 1,3-butadiene was charged into the autoclave through molecular sieves.
Stirred. Next, water shown in Table 2 was added, and the mixture was stirred and dissolved for 30 minutes. Into this FB (solvent + butadiene), hydrogen gas was added at 20 ° C. and 1 atm.
00 mL was injected. Next, triethylaluminum (a 1 mmol / mL toluene solution) was added in the amount shown in Table 2, and after stirring for 10 minutes, cyclopentadienyl vanadium trichloride (CpVCl ₃ ) was added in the order shown in Table 3.
(0.005 mmol / mL toluene solution) 2.5 m
l, triphenyl carbonium tetrakis (pentafluorophenyl) borate - DOO _{(Ph 3 CB (C 6 F} 5) 4)
(0.0025 mmol / mL toluene solution) 10 m
were added in the order shown in Table 1, and polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes. After polymerization, 2,6-di-t-butyl-p-
An equivalent mixed solution of ethanol and heptane containing a small amount of cresol was charged, the pressure was released, and the mixture was poured into ethanol to precipitate a polymer, which was filtered and dried. Tables 3 and 4 show the polymerization results.

(Embodiments 6 to 10)
The inside of the reactor was replaced with nitrogen, and 1.0 L of 1,3-butadiene was charged into the reactor through molecular sieves and stirred. Hydrogen gas is accumulated by mass flow meter for 20
200 mL was injected at a pressure of 1 ° C. and 1 atm. Next, triethylaluminum (1 mmol / mL toluene solution)
Was added in the amount shown in Table 2, and the mixture was stirred for 10 minutes. Further, the amount of water shown in Table 2 was added while stirring. After stirring for 30 minutes, cyclopentadienyl vanadium trichloride (CpV
Cl ₃ ) (a 0.005 mmol / mL toluene solution)
2.5 ml, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C
₆ F ₅ ) ₄ ) (a solution of 0.0025 mmol / mL in toluene) (10 ml) was added in the order shown in Table 3, and the polymerization temperature was 40 ° C.
For 30 minutes. After the polymerization, a mixed solution of an equivalent amount of ethanol and heptane containing a small amount of 2,6-di-tert-butyl-p-cresol was charged, the pressure was released, and the mixture was poured into ethanol to precipitate a polymer. , Filtered and dried. Tables 3 and 4 show the polymerization results.

(Comparative Examples 1 and 2) The same operation as in Examples 1 to 5 was performed to obtain FB1L with adjusted moisture. This FB
Inside, 200 mL of hydrogen gas was injected at 20 ° C. and 1 atm with a cumulative mass flow meter. Then, in the order shown in Table 3, 2.5 ml of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) (a toluene solution of 0.005 mmol / mL), triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃₎ CB
10 ml of (C ₆ F ₅ ) ₄ ) (a solution of 0.0025 mmol / mL in toluene) was added, and triethylaluminum (a solution of 1 mmol / mL in toluene) was added in the amount shown in Table 2. After stirring for 10 minutes, the polymerization temperature was increased to 40 ° C. Polymerization was carried out at 30 ° C for 30 minutes. After the polymerization, an equivalent mixed solution of ethanol and heptane containing a small amount of 2,6-di-tert-butyl-p-cresol was charged, the pressure was released, and the mixture was poured into ethanol to precipitate a polymer. , Filtered and dried. Tables 3 and 4 show the polymerization results.

Comparative Examples 3 and 4 Triethylaluminum (1 mmol / mL toluene solution) was added in the same manner as in Examples 6 to 10 in the amounts shown in Table 2. After stirring for 10 minutes, cyclopentadienyl vanadium trichloride (CpVCl ₃ ) (0.005 mmol) was used in the order shown in Table 3.
l / mL of toluene solution) 2.5 ml, triphenyl carbonium tetrakis (pentafluorophenyl) borate - DOO _{(Ph 3 CB (C 6 F} 5) 4) (0.0025mmol
/ Ml of toluene solution) and 10 ml of
Of water was added with stirring. After stirring for 10 minutes, polymerization was performed at a polymerization temperature of 40 ° C. for 30 minutes. After polymerization, ethanol containing a small amount of 2,6-di-t-butyl-p-cresol
An equivalent mixed solution of toluene and heptane was charged, the pressure was released, and the mixture was poured into ethanol to precipitate a polymer, which was filtered and dried.
Tables 3 and 4 show the polymerization results.

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

The present invention provides a method for producing a conjugated diene polymer having a controlled microstructure with high polymerization activity using a metallocene complex of a transition metal compound of Group V of the periodic table.

Continuation of the front page (72) Inventor Tomonori Suzuki 8-1 Goi South Coast, Ichihara City, Chiba Pref. BC27B CA02C CA32C CB65C CB87C CB94C EA01 EB02 EB04 EB05 EB06 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB16 EB17 EB18 EB21 EB26 EC01 EC02 FA01 FA07 FA09 GA03 GA11

Claims (2)

[Claims] 1. A metallocene complex of a transition metal compound of Group 5 of the periodic table, (B) an ionic compound of a non-coordinating anion and a cation, (C) an organoaluminum compound, and (D) water. A method for producing a conjugated diene polymer, comprising performing bulk polymerization when polymerizing a conjugated diene compound using a catalyst obtained from the above. 2. A metallocene complex of a transition metal compound of Group 5 of the periodic table, (B) an ionic compound of a non-coordinating anion and a cation, (C) an organoaluminum compound,
And (D) a method for producing a conjugated diene polymer, which comprises performing bulk polymerization when polymerizing a conjugated diene compound using a catalyst comprising water.