JPH09316122A - Production of conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control the molecular weight of a polymer without detriment to polymerization activity in the production of a conjugated diene polymer having a controlled microstructure by using a catalyst system comprising a metallocene complex of a transition metal compound. SOLUTION: A conjugated diene compound is polymerized in the presence of hydrogen and a catalyst obtained from a metallocene complex of a group V transition metal compound in the periodic table and an ionic compound comprising a non-coordinate anion and a cation and/or an aluminoxane to produce a conjugated diene polymer. According to this process, a polybutadiene having an intrinsic viscosity [η] of 0.1-20 and a weight-average molecular weight of 10,000-4,000,000 can be produced.. This polybutadiene can be desirably used as an impact modifier for polystyrene.

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 give polymers having various microstructures by using a polymerization catalyst. A method for producing a high-cis structure polybutadiene using a cobalt compound and an organoaluminum compound is known, but polybutadiene containing a 1,2-structure in a high-cis structure in an appropriate amount imparts impact resistance to a vinyl aromatic polymer. Agents are expected.

In recent years, various olefin polymerizations using metallocene type complexes as catalysts have been actively developed, and the polymerization of conjugated dienes has also been studied.

Polymerization of a conjugated diene using a metallocene type complex is described, for example, in Macromol. Symp., 89, 383 (19).
95), a catalyst system composed of cyclopentadienyl titanium trichloride (CpTiCl ₃ ) which is a group IV transition metal compound of the periodic table and methylalumoxane has been reported, but it has a problem of low polymerization activity. .

Also, Polymer vol.37 (2) p.363 (1996)
For the high cis structure, a catalyst composed of a vanadium (III) compound such as Cp'VCl ₂ or Cp ₂ VCl, which is a metallocene-type complex of a transition metal of Group V of the periodic table, and methylalumoxane was used, and A method for producing polybutadiene containing 100% of 1,2-structure has been reported.

As a method for controlling the molecular weight in the butadiene polymerization, in the high cis polybutadiene polymerization using the above cobalt compound-organoaluminum compound, for example, Japanese Patent Publication No. 41-5474 discloses a method of adding cyclooctadiene. There is.

However, in a catalyst system using a metallocene-type complex of a transition metal compound of Group V of the Periodic Table, addition of the above-mentioned cyclooctadiene to the polymerization system causes a decrease in the polymerization activity and the resulting conjugated diene polymer. There is a problem that the microstructure of the changes.

[0008]

In a method for producing a conjugated diene polymer having a controlled microstructure by a catalyst system using a metallocene type complex of a transition metal compound of Group V of the periodic table, the polymerization activity is decreased. It is an object of the present invention to provide a method for controlling the molecular weight of a conjugated diene polymer without using it.

[0009]

The present invention provides (A) a metallocene-type complex of a Group V transition metal compound of the periodic table, and (B) an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane. Using the catalyst obtained from
The present invention relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound in the presence of hydrogen.

The present invention also provides (A) a metallocene complex of a Group V transition metal compound of the periodic table, and (B) a catalyst comprising an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane. The present invention relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound in the presence of hydrogen.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) Metallocene-type complexes of Group V transition metal compounds of the periodic table include (1) RMX ₃ · L _a (2) R _n MX _3-n · L _a (3) RM (O) X ₂ · L Examples thereof include compounds represented by the general formula, such as _a (4) R _n MX _3-n (NR ′) (5) MX ₃ (NR ′). In the above formula, n is 1 to 2 and a is 0, 1 or 2.

M represents a group V transition metal compound of the periodic table. Specifically, it is vanadium (V), niobium (Nb), or tantalum (Ta), and the preferred metal is 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, the substituted indenyl group or the substituted fluorenyl group include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl and hexyl. And straight chain aliphatic hydrocarbon groups or branched aliphatic hydrocarbon groups, aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, benzyl, and hydrocarbon groups containing a silicic atom such as trimethylsilyl. Further, those in which a cyclopentadienyl ring is partly 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. Among 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 halogen include a fluorine atom,
Examples thereof include chlorine atom, bromine atom and iodine atom.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include linear groups such as methyl, ethyl, propyl, iso-propyl, 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.
Of these, 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 atom, bromine atom, methyl, ethyl, butyl, methoxy, ethoxy, dimethylamino, diethylamino and the like are preferable.

L is a Lewis base, which is a general Lewis basic inorganic or organic compound capable of coordinating with 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 methyl, ethyl, propyl, iso-propyl, sec-butyl, t-butyl, hexyl, octyl, neopentyl and other straight-chain aliphatic hydrocarbon groups or branched aliphatic hydrocarbon groups, Examples thereof include aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, benzyl, methylphenylmethyl, dimethylphenyl, 2,6-dimethylphenyl, and 3,4-dimethylphenyl. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included.

(A) Metallocene type complexes of Group V transition metal compounds 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 in which M is vanadium,
R ₂ VX · L _a, vanadium compounds such as RVX ₂ · L _a is preferable.

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

(I) Examples include cyclopentadienyl vanadium trichloride. Mono-substituted cyclopentadienyl vanadium trichloride, for example, methyl cyclopentadienyl vanadium trichloride, ethyl cyclopentadienyl vanadium trichloride, propyl cyclopentadienyl vanadium trichloride,
Isopropylcyclopentadienyl vanadium trichloride, t-butylcyclopentadienyl vanadium trichloride, (1,1-dimethylpropyl) cyclopentadienyl vanadium trichloride, (1,1-dimethylbenzyl) cyclopentadienyl vanadium trichloride Chloride, (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 can be mentioned.

(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-Tri-substituted cyclopentadienyl vanadium trichloride, for example, (1,2,3-trimethylcyclopentadienyl) vanadium trichloride, etc. may be mentioned.

(Iv) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride, for example, (1,2,4-trimethylcyclopentadienyl) vanadium trichloride, etc. may be mentioned.

(V) Tetra-substituted cyclopentadienyl vanadium trichloride, such as (1,2,3,4-tetramethylcyclopentadienyl) vanadium trichloride, (1,2,3,4-tetraphenylcyclo) Pentadienyl)
Vanadium trichloride and the like can be mentioned.

(Vi) Penta-substituted cyclopentadienyl vanadium trichloride, such as (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 may be mentioned. Substituted indenyl vanadium trichloride, for example, (2-methylindenyl) vanadium trichloride, (2-trimethylsilylindenyl) vanadium trichloride and the like can be mentioned.

(Viii) Indenyl vanadium trichloride may be mentioned.

(Ix) A monoalkoxide in which the chlorine atom of the compounds of (i) to (viii) is substituted with an alkoxy group or a methyl group,
Dialkoxide, trialkoxide and the like.
For example, trimethylsilylcyclopentadienyl vanadium triter-butoxide, trimethylcyclopentadienyl vanadium tri-iso-propoxide, trimethylsilylcyclopentadienyl vanadium dimethoxychloride, trimethylsilylcyclopentadienyl vanadium diiso-propoxycyclolide, trimethylsilylcyclopentadienyl Vanadium diter-butoxycyclolide, trimethylsilylcyclopentadienyl vanadium diphenoxycyclolide, trimethylsilylcyclopentadienyl vanadium iso-propoxydichloride, trimethylsilylcyclopentadienyl vanadium ter-butoxydichloride, trimethylsilylcyclopentadienyl vanadium phenoxydichloride

(X) A methyl form in which the chlorine atom of (ix) is substituted with a methyl group can be mentioned.

(Xi) R may be a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethyl (eta ⁵ - cyclopentadienyl) vanadium dichloride, (t-butylamido) dimethyl (trimethyl- - eta ⁵ - cyclopentadienyl) vanadium dichloride, (t-butylamido) dimethyl (tetramethyl - η ^5-
(Cyclopentadienyl) vanadium dichloride.

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

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

(Xvi) Compounds in which the monochloro compound of (xiii) is substituted with a methyl group can be mentioned.

Examples thereof include amides (xv) (i) to (viii) in which the chlorine atom is replaced with 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.

Examples include (xvi) and (xv) which are methyl compounds in which the chlorine atom is replaced with a methyl group.

Among the specific compounds represented by R _n MX _3-n · L _a , compounds having n = 1 include 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, Indenyl vanadium dichloride, (2-methylindenyl) vanadium dichloride, (2-trimethylsilylindenyl) vanadium dichloride, dichlorides such as fluorenyl vanadium dichloride, or dimethyl compounds in which the chlorine atom of these compounds is replaced with a methyl group And so on.

Those in which R and X are bound by a hydrocarbon group or a silyl group are also included. For example, (t-butylamide)
Dimethylsilyl (eta ⁵ - cyclopentadienyl) vanadium dichloride, (t-butylamido) dimethylsilyl (tetramethyl-eta ⁵ - cyclopentadienyl) methyl chlorine atom of the amide chloride of vanadium chloride, or these compounds And amides substituted with a group.

Cyclopentadienyl vanadium dimethoxide, cyclopentadienyl vanadium diiso-propoxide, cyclopentadienyl vanadium diter-butoxide, cyclopentadienyl vanadium diphenoxide, cyclopentadienyl vanadium methoxy chloride, cyclo Examples include alkoxides such as pentadienyl vanadium iso-propoxycyclolide, cyclopentadienyl vanadium ter-butoxycyclolide, and cyclopentadienyl vanadium phenoxycyclolide, or methyl compounds obtained by substituting the chlorine atom of these compounds with a methyl group. .

Examples of bisamide compounds include (cyclopentadienyl) (bisdiethylamido) vanadium, (cyclopentadienyl) (bisdiiso-propylamido) vanadium, and (cyclopentadienyl) (bisdin-octylamido) vanadium. To be

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

Among the specific compounds represented by R _n MX _3-n · L _a , compounds having n = 2 include dicyclopentadienyl vanadium chloride, 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)
Chlorides of vanadium chloride, diindenyl vanadium chloride, bis (2-methylindenyl) vanadium chloride, bis (2-trimethylsilylindenyl) vanadium chloride, difluorenylvanadium chloride, etc., or the chlorine atom of these compounds is methylated. Examples include a methyl group substituted with a group.

Dicyclopentadienyl vanadium methoxide, dicyclopentadienyl vanadium iso-propoxide, dicyclopentadienyl vanadium ter-butoxide, dicyclopentadienyl vanadium phenoxide, dicyclopentadienyl diethylamide vanadium, di Examples include cyclopentadienyldiiso-propylamidovanadium and dicyclopentadienyldi-n-octylamidovanadium.

Those in which R is bound by a hydrocarbon group or a silyl group are also included. For example, chloride bodies such as dimethylbis (η ⁵ -cyclopentadienyl) silane vanadium chloride and dimethylbis (tetramethyl-η ⁵ -cyclopentadienyl) silane vanadium chloride,
Alternatively, methyl compounds in which the chlorine atom of these compounds is substituted with a methyl group may be mentioned.

Specific compounds 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 Such as fluorenyl oxovanadium dichloride and the like. 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.

Specific compounds 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) (phenylimido) vanadium dichloride, (1,3-dimethyl Cyclopentadienyl) (phenylimido) vanadium dichloride, (1-
Methyl-3-butylcyclopentadienyl) (phenylimido) vanadium dichloride, (pentamethylcyclopentadienyl) (phenylimido) vanadium dichloride, indenyl (phenylimido) vanadium dichloride, 2-methylindenyl (phenylimido) vanadium Dichloride, fluorenyl (phenylimide)
Examples thereof include dichlorides such as vanadium dichloride.

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 (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.

Those in which R is bound 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.

Specific compounds represented by MX ₃ (NR ′) include (methylimido) vanadium trichloride, (phenylimido) vanadium trichloride, vanadium (phenylimido) trimethoxide, (phenylimido) vanadium dimethoxy. Examples thereof include chloride and (phenylimido) vanadium methoxydichloride. (Dimethylamido) methylimidovanadium dichloride, bis (dimethylamido) methylimidovanadium chloride, tris (dimethylamido) methylimidovanadium and the like can be mentioned.

Among the component (B) of the present invention, examples of the non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation include, for example, tetra (phenyl) borate and 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-dicarbaundecaborate, tetrafluoroborate, hexaflu Rohosufeto 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 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 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 -
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 these, 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 kinds.

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, 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 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 preferably used.

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

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 metallocene-type complex of the component (A) to the aluminoxane of the component (B) is preferably 1: 1 to.
The ratio is 1: 10000, more preferably 1: 1 to 1: 5000.

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

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

The order of adding the catalyst components is not particularly limited, but they can be added, for example, in the following order. The component (A) is added to a contact mixture of the conjugated diene compound monomer to be polymerized and the component (B). The component (A) is added to a contact mixture in which the conjugated diene compound monomer to be polymerized, the component (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.

Here, the conjugated diene compound monomer to be polymerized 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.

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. You may use these monomer components in combination of 2 or more type.

In addition to the conjugated diene, 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, using the above catalyst,
The conjugated diene compound is polymerized in the presence of hydrogen.

The amount of hydrogen present is preferably 50 mmol or less, or 1.2 L or less at 20 ° C. and 1 atm, more preferably 0.005 to 20 mmol, or 20 ° C. and 1 atm with respect to 1 mol of the conjugated diene. And 0.001 to 0.48L. Further, hydrogen may be continuously introduced into the polymerization tank.

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-
Examples thereof include hydrocarbon solvents such as olefin hydrocarbons such as butene, mineral spirit, solvent naphtha, and kerosene, and halogenated hydrocarbon solvents such as methylene chloride. 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.

The polymerization temperature is preferably in the range of -100 to 100 ° C, particularly preferably in the range of -50 to 80 ° C. 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 processes are carried out.

By using the above-mentioned polymerization method of the present invention, the 1,2-structure content is 4 to 30%, preferably 5 to 25%,
More preferably 5 to 20%, the cis-1,4-structure content is 65 to
It is possible to produce polybutadiene having a content of trans-1,4-structure of 95%, preferably 70 to 95%, of 5% or less, preferably 4.5% or less.

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

These polybutadienes can be preferably used as impact resistance imparting agents for polystyrene.

[0091]

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

The molecular weights Mw and Mn of polybutadiene are
It was determined by gel permeation chromatography (GPC). The [η] of polybutadiene was measured at 30 ° C. in a toluene solution.

(Examples 1 to 3) The inside of an autoclave having an internal capacity of 1.5 L was replaced with nitrogen, and 300 mL of toluene and 1,3-
Charge 62 g of butadiene and stir. Then, a pressure vessel having an internal volume corresponding to the amount of hydrogen shown in Table 1 was filled with hydrogen gas at 20 ° C. at 1 atm and injected with nitrogen pressure. Then, a toluene solution of 5 mmol of alumoxane (MMAO manufactured by Toso Akzo Co., Ltd.) prepared by using a mixture of trimethylaluminum and tributylaluminum as a raw material, 2 ml of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) 0.
01 mmol was added, and polymerization was carried out at a polymerization temperature of 40 ° C. for 60 minutes. After the polymerization, ethanol containing a small amount of 2,6-di-t-butyl-p-cresol was added to precipitate a polymer, followed by filtration and drying. The polymerization results are shown in Tables 1 and 2.

Comparative Example 1 The same procedure as in Example 1 was carried out except that hydrogen gas was not used. The polymerization results are shown in Tables 1 and 2.

(Examples 4 to 7) The autoclave having an internal capacity of 1.5 L was replaced with nitrogen, and 300 mL of toluene and 1,3-
Charge 62 g of butadiene and stir. Next, a pressure vessel having an internal volume corresponding to the amount of hydrogen shown in Table 4 was filled with hydrogen gas at 20 ° C. at 1 atm and injected under nitrogen pressure. Then 0.5 ml of a toluene solution of 0.5 mmol of triisobutylaluminum,
Triphenyl carbonium tetrakis (pentafluorophenyl) borate - DOO _{(Ph 3 CB (C 6 F} 5) 4) in toluene 1.5ml of 0.0075 mmol, cyclopentadienyl vanadium trichloride (CpVCl ₃₎ 0.005mmol toluene solution 0.1 ml
Was added and polymerization was carried out at a polymerization temperature of 40 ° C. for 20 minutes. After polymerization,
Ethanol containing a small amount of 2,6-di-t-butyl-p-cresol was added to precipitate a polymer, which was filtered and dried. The polymerization results are shown in Tables 3 and 4.

Comparative Example 2 The same procedure as in Example 4 was carried out except that hydrogen gas was not used. The polymerization results are shown in Tables 3 and 4.

(Examples 8 to 12) The inside of an autoclave having an internal capacity of 1.5 L was replaced with nitrogen, 300 mL of cyclohexane and 62 g of 1,3-butadiene were charged and stirred. Then
A pressure vessel having an internal volume corresponding to the amount of hydrogen shown in Table 5 was filled with hydrogen gas at 20 ° C. at 1 atm and injected with nitrogen pressure. Then triethylaluminum 0.25 mmol in toluene solution
0.25 ml, triphenyl carbonium tetrakis (pentafluorophenyl) borate - DOO _{(Ph 3 CB (C 6 F} 5) 4) 0.01mm
2 ml of toluene solution of ol, 0.005 mmol of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) in toluene solution
0.1 ml was added and the polymerization was carried out at a polymerization temperature of 40 ° C. for 60 minutes. After the polymerization, ethanol containing a small amount of 2,6-di-t-butyl-p-cresol was added to precipitate a polymer, followed by filtration and drying. Tables 5 and 6 show the polymerization results.

(Comparative Example 3) The procedure of Example 8 was repeated except that hydrogen gas was not used. Tables 5 and 6 show the polymerization results.

Comparative Examples 4 to 6 The hydrogen gas was changed to a toluene solution of 1,5-cyclooctadiene in the amount shown in Table 7,
The same procedure as in Example 8 was performed except that the addition was performed with a syringe. The polymerization results are shown in Tables 7 and 8.

Comparative Examples 7 and 8 The same procedure as in Example 8 was carried out except that the amount of hydrogen gas was changed to the toluene solution of 1,2-butadiene shown in Table 9 and added by a syringe. The polymerization results are shown in Tables 9 and 10.

(Example 13) 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 33 ml of butadiene, 1.5 μmol of (CH ₃ ) ₂ NH (C ₆ H ₅ ) B (C ₆ F ₅ ) ₄ ) was added, and cyclopentadienyl oxo was introduced while introducing hydrogen at a rate of 5 ml / min. 1.0 μmol of vanadium dichloride 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 white polybutadiene. The catalytic activity was 8,100 g / mmol-Vh. The microstructure of polybutadiene is cis 87.2%,
It was trans 3.6% and vinyl 9.2%. Also, Mw
It was 0.502 × 10 ⁶ , and Mw / Mn was 1.59.

Example 14 Polymerization was carried out under the same conditions as in Example 13 except that hydrogen was introduced at a rate of 20 ml / min. Polymerization was stopped with an ethanol solution containing HCl, filtered and dried to obtain white polybutadiene. 5,200 catalytic activity
It was g / mmol-Vh. The microstructure of polybutadiene was cis 86.7%, trans 5.9%, vinyl 7.4%. The Mw was 0.019 × 10 ⁶ and the Mw / Mn was 2.86.

(Comparative Example 9) The procedure of Example 13 was repeated except that hydrogen gas was not used. Catalytic activity is 10,200 g / mm
It was ol-Vh. The microstructure of polybutadiene was cis 88.9%, trans 1.7%, and vinyl 9.4%. The Mw was 2.917 × 10 ⁶ and the Mw / Mn was 2.96.

(Examples 15 and 16) An internal capacity of 1.7 L
The inside of the Toclave was replaced with nitrogen, and 250 mL of toluene and
Charge 93g (1.72mol, 150ml) of 1,3-Butadiene
Stir. Then, the contents corresponding to the hydrogen amount shown in Table 11
The pressure vessel of the product is filled with hydrogen gas at 1 atm and 20 ℃
Injected. Then triethylaluminum 0.75m
mol toluene solution, triphenylcarbonium tetra
Kiss (pentafluorophenyl) borate (Ph _ThreeCB (C
₆F_Five)_Four) 0.0075mmol toluene solution, cyclopentadiene
Nylvanadium trichloride (CpVCl_Three) 0.005 mmol
Add toluene solution and polymerize at polymerization temperature of 40 ℃ for 60 minutes.
Was. After polymerization, a small amount of 2,6-di-t-butyl-p-cresol was included.
Add the ethanol to have the polymer precipitate, filter,
Dried. The polymerization results are shown in Tables 11 and 12.

(Examples 17 to 24) Internal capacity of 1.7 L
The inside of the Toclave was replaced with nitrogen, and 250 mL of toluene and
Charge 93 g (1.72 mol, 150 ml) of 1,3-butadiene and stir. Then, a hydrogen amount gas for increasing the system pressure by the pressure shown in Table 11 was injected. Then, a solution of triethylaluminum 0.75 mmol in toluene, triphenylcarbonium tetrakis (pentafluorophenyl) borane
Solution of (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 0.0075 mmol in toluene, cyclopentadienyl vanadium trichloride (CpVCl ₃ ) 0.
A 005 mmol toluene solution was added, and polymerization was carried out at a polymerization temperature of 40 ° C. for 60 minutes. After polymerization, 2,6-di-t-butyl-p-creso-
Polymer containing a small amount of polymer was added to precipitate a polymer, which was filtered and dried. Tables 11 and 12 show the polymerization results.

(Comparative Example 10) 1,3 without using hydrogen gas
-Butadiene 62 g (1.15 mol), triethylaluminum 0.5 mmol, Example 15 except that the polymerization time was 20 minutes.
I went the same way. Tables 11 and 12 show the polymerization results.

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[Table 1]

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[Table 2]

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[Table 3]

[0110]

[Table 4]

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[Table 5]

[0112]

[Table 6]

[0113]

[Table 7]

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[Table 8]

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[Table 9]

[0116]

[Table 10]

[0117]

[Table 11]

[0118]

[Table 12]

[0119]

INDUSTRIAL APPLICABILITY In a method for producing a conjugated diene polymer using a metallocene type complex of a transition metal compound of Group V of the periodic table, a method for adjusting the molecular weight of a conjugated diene polymer having a controlled microstructure to a desired range is provided. provide.

Claims (2)

[Claims] 1. A catalyst obtained from (A) a metallocene complex of a transition metal compound of Group V of the periodic table and (B) an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane, A method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound in the presence of hydrogen. 2. A catalyst comprising (A) a metallocene-type complex of a transition metal compound of Group V of the periodic table and (B) an ionic compound of a non-coordinating anion and / or an aluminoxane, and hydrogen. A method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound in the presence of: