JPH11199617A - Polymerization catalyst for copolymer and production of copolymer using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization catalyst having high long-term storage stability and reproducibility of the catalytic activity and excellent heat-stability for industrial use by combining a trivalent group 4 metal complex with a metallic compound or a cation generation agent each having respectively specific structure. SOLUTION: This catalyst contains (A) a complex expressed by the formula [M is a group 4 transition metal; the 5-membered ring is a (substituted) cyclopentadienyl; R<1> to R<4> are each H, a 1-12C alkyl, an alkenyl or the like; Y is C, Si or Ge; Z is N, P, S or O; X<1> , X<2> and R<4> to R<7> are each H, a 1-12C alkyl, an alkoxy or the like; (m) is 1-3; (n) is an integer of 1-3 corresponding to the valence of the bonded heteroatom -1] and preferably further (B) an alkylaluminumoxy compound and/or (C) a cation generation agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel complex catalyst for polymerization and a method for producing an ethylene-vinyl aromatic monomer copolymer using the catalyst.

[0002]

2. Description of the Related Art As a copolymerization catalyst of ethylene and a vinyl aromatic monomer, a group 4 tetravalent metal coordination having a geometric shape constrained in Japanese Patent Application Laid-Open Nos. 3-163088 and 7-70223 is disclosed. The complex is known as a catalyst system having high activity and excellent copolymerizability. However, these complex catalyst systems have poor stability at a high temperature of 50 ° C. or higher, and have poor long-term storage stability and reproducibility of activity of the complex. It can be said that what is left.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to find a catalyst system which is more heat-stable than conventional complexes in industrial use and has a long-term storage stability and a high reproducibility of the activity. It is.

[0004]

According to the present invention, a group 4 trivalent complex having a specific structure has higher thermal stability than a conventional complex, and (A) a group 4 trivalent complex having a specific structure and (B) ) Based on the surprising fact that, in combination with a metal compound having a specific structure or a cation generator, the long-term storage stability is better and the reproducibility of polymerization activity is far superior to conventional complex catalyst systems. It was done.

That is, the present invention provides: [1] a polymerization catalyst, wherein the catalyst (A) component comprises a complex represented by the following general formula (1):

Embedded image (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. )

[2] A polymerization catalyst comprising a component (A) containing a complex represented by the following general formula (1) and a component (B) and / or a component (C): (A)

Embedded image (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. (B) Alkyl aluminum oxy compound (C) Cation generator

[3] A polymerization catalyst comprising a catalyst (A) and a component (B) and / or a component (C) and a component (D) containing a complex represented by the following general formula (1): (A)

Embedded image (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. (B) alkyl aluminum oxy compound (C) cation generator (D) alkyl aluminum compound

[4] A catalyst containing a complex represented by the following general formula (1): component (A) and component (B) and / or component (C) and / or component (D) and component (E). (A)

Embedded image (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. (B) alkyl aluminum oxy compound (C) cation generator (D) alkyl aluminum compound (E) alkyl alkali metal and / or alkyl alkaline earth metal compound

[5] The pseudopolymer of ethylene and styrene, wherein the copolymer polymerized with the above polymerization catalysts [1] to [4] contains 98.6 to 53 mol% of ethylene and 1.4 to 47 mol% of styrene. A method for producing a copolymer characterized by being a random copolymer. As a copolymerization catalyst of ethylene and a vinyl aromatic monomer, JP-A-Hei 3
There is a metal coordination complex having a constrained geometry, such as -163088 and JP-A-7-70223,
These complex catalyst systems have been found to have poor thermal stability at temperatures above 50 ° C. In addition, there is a problem that the long-term storage stability of the complex and the reproducibility of the activity are not sufficient.In terms of industrial use, the complex has a copolymerization activity equal to or higher than that of the above complex, and can be easily synthesized and handled. An easy complex was desired.

The present inventors have conducted intensive studies on a novel complex catalyst system which can solve the above-mentioned problems. As a result, (A) a half metallocene complex having a specific structure is easily synthesized, and the thermal stability of the complex is improved. And (A) and (B) an aluminum oxy compound and / or (C) a cation generator in combination with (A), (B) and / or (C), and further (D). The system combining the components and the system combining the components (A), (B) and / or (C) and / or (D) and the component (E) have excellent copolymerization activity, a wide polymerization temperature range, The present inventors have found that the activity is hardly reduced by temperature and the activity reproducibility is high, and the present invention has been completed.

The polymerization catalyst component (A) according to the present invention is represented by the following general formula (1).

Embedded image In the formula, M is a Group 4 trivalent transition metal, which is Ti, Zr, or Hf. The five-membered ring includes a cyclopentadienyl group and a substituted cyclopentadienyl group, including an indenyl group, a fluorenyl group and the like. M and the substituted cyclopentadienyl group are η
The carbons of the 5-membered ring are π-bonded at ⁵ and are respectively equivalent. R ^{1 to} R ⁴ may be the same or different, and any two or three of hydrogen or a C ^{1 to} C ¹² alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring. The ring may include those having an aromatic property including a conjugated double bond such as indenyl and fluorenyl.

Y is an alkylene, silylene or germylene group of carbon or Si or Ge; R ⁵ and R ⁶ may be the same or different;
R ⁵ and R ⁶ in the alkyl group, alkoxy group, alkenyl group, allyloxy group, and aryl group described above may be bonded to each other to form a heterocyclic ring containing Y. m is an integer of 1 to 3. Z is any one of N, P, S, and O elements, and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. R ⁷ may be the same or different, and is made of hydrogen or a C1 to C12 alkyl group, alkoxy group, aryl group, allyloxy group, or halogen. n is a number corresponding to the valence of the heteroatom-1 bonded by an integer of 1 to 3. Specifically, Z (R ⁷ ) n includes a compound represented by the following general formula (2).

[0013]

Embedded image (However, R ⁸ and R ⁹ may be the same or different, and are each composed of a C1 to C12 alkyl group, alkoxy group, aryl group, allyloxy group, and halogen.) X ¹ and X ² are the same. However, they may be different from each other and include hydrogen or a C1 to C12 alkyl group, alkoxy group, aryl group, allyloxy group, or halogen.

In the general formulas (1) and (2), R ¹
Specific examples of the alkyl group, aryl group and alkoxy group of R ⁹ to R ⁹ , alkyl and aryl of the aryloxy group include hydrogen, methyl, ethyl, propyl, isopropyl,
n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl,
2-methylbutyl, 1,2-dimethylpropyl, neopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl,

3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,1-ethylmethylpropyl , 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl,
1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1, -Ethylpentyl,

1-propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-ethylmethylbutyl, 1,1-diethylpropyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4 -Dimethylpentyl, 1, -ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 4-methylcyclohexyl, 3-
Methylcyclohexyl, cycloheptyl, 1,1,2-
Trimethylbutyl, 1,1,3-trimethylbutyl,
2,2,1-trimethylbutyl, 2,2,3-trimethylbutyl, 3,3,1-trimethylbutyl, 3,3,2
-Trimethylbutyl, 1,1,2,2-tetramethylpropyl, n-octyl,

1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, isooctyl, 1-ethylhexyl 2-
Ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethyl Hexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 3,4-
Dimethylhexyl, 2,5-dimethylhexyl, 3,5
-Dimethylhexyl, 1,1-methylethylpentyl,
1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-
Ethyl-1-methylpentyl,

2,2-ethylmethylpentyl, 3,3-
Ethyl methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-4
-Methylpentyl, 3-ethyl-2-methylpentyl,
1,1-diethylbutyl, 2,2-diethylbutyl,
1,2-diethylbutyl, 1,1-methylpropylbutyl, 2-methyl-1-propylbutyl, 3-methyl-1-
Propylbutyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 3,4-dimethylcyclohexyl,
1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,1,4-trimethylpentyl, 2,
2,1-trimethylpentyl, 2,2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 3,3
1-trimethylpentyl, 3,3,2-trimethylpentyl, 3,3,4-trimethylpentyl, 1,2,3-
Trimethylpentyl, 1,2,4-trimethylpentyl,

1,3,4-trimethylpentyl, 1,
2,3-trimethylpentyl, 1,2,4-trimethylpentyl, 1,3,4-trimethylpentyl, 1,1,
2,2-tetramethylbutyl, 1,1,3,3-tetramethylbutyl, 1,1,2,3-tetramethylbutyl,
2,2,1,3-tetramethylbutyl, 1-ethyl-
1,2-dimethylbutyl, 2-ethyl-1,2-dimethylbutyl, 1-ethyl-2,3-dimethylbutyl, n-
Nonyl, isononyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl,
5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl,

3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl 1,1-dimethylheptyl,
2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 5,5-dimethylheptyl, 6,6-dimethylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, 2,4-dimethylheptyl, 1,5-dimethylheptyl, 1,6-dimethylheptyl, 2,3-dimethylheptyl, 2,4-dimethylheptyl, 2,5-dimethylheptyl, 2,6-dimethylheptyl, 3, 4-dimethylheptyl, 3,5-
Dimethylheptyl, 3,6-dimethylheptyl, 4,5
-Dimethylheptyl, 4,6-dimethylheptyl, 5,
6-dimethylheptyl, 1,1,2-trimethylhexyl,

1,1,3-trimethylhexyl, 1,
1,4-trimethylhexyl, 1,1,5-trimethylhexyl, 2,2,1-trimethylhexyl, 2,2
3-trimethylhexyl, 2,2,4-trimethylhexyl, 2,2,5-trimethylhexyl, 3,3,1-
Trimethylhexyl, 3,3,2-trimethylhexyl, 3,3,4-trimethylhexyl, 3,3,5-trimethylhexyl, 4,4,1-trimethylhexyl,
4,4,2-trimethylhexyl, 4,4,3-trimethylhexyl, 4,4,5-trimethylhexyl, 5,
5,1-trimethylhexyl, 5,5,2-trimethylhexyl, 5,5,3-trimethylhexyl, 5,5
4-trimethylhexyl, 1,2,3-trimethylhexyl, 2,3,4-trimethylhexyl,

3,4,5-trimethylhexyl, 1,
3,4-trimethylhexyl, 1,4,5-trimethylhexyl, 2,4,5-trimethylhexyl, 1,2,2
5-trimethylhexyl, 1,2,4-trimethylhexyl, 1,1-ethylmethylhexyl, 2,2-ethylmethylhexyl, 3,3-ethylmethylhexyl, 4,
4-ethylmethylhexyl, 5,5-ethylmethylhexyl, 1-ethyl-2-methylhexyl, 1-ethyl-
3-methylhexyl, 1-ethyl-4-methylhexyl, 1-ethyl-5-methylhexyl, 2-ethyl-1
-Methylhexyl, 3-ethyl-1-methylhexyl,
3-ethyl-2-methylhexyl, 1,1-diethylpentyl, 2,2-diethylpentyl, 3,3-diethylpentyl, 1,2-diethylpentyl, 1,3-diethylpentyl, 2,3-diethylpentyl 1,1,1-methylpropylpentyl, 2,2-methylpropylpentyl,

1-methyl-2-propylpentyl n-decyl, isodecyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyloctyl, 1,1-dimethyloctyl, 2,2-dimethyloctyl, 3,3-dimethyloctyl, 4,4-
Dimethyloctyl, 5,5-dimethyloctyl, 6,6
-Dimethyloctyl, 7,7-dimethyloctyl, 1,
2-dimethyloctyl, 1,3-dimethyloctyl,
1,4-dimethyloctyl, 1,5-dimethyloctyl, 1,6-dimethyloctyl, 1,7-dimethyloctyl, 2,3-dimethyloctyl, 2,4-dimethyloctyl, 2,5-dimethyloctyl,

2,6-dimethyloctyl, 2,7-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 3,7-dimethyloctyl
Dimethyloctyl, 4,5-dimethyloctyl, 4,6
-Dimethyloctyl, 4,7-dimethyloctyl, 5,
6-dimethyloctyl, 5,7-dimethyloctyl, n
-Undecyl, n-dodecyl, phenyl, benzyl, p
-Tolyl, m-tolyl, xylyl, mesitylyl, 2,6
-Dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl,
2,4,6-triisopropylphenyl, naphthyl, o
-Isopropoxyphenyl and the like.

Examples of the aluminum oxy compound of the catalyst component (B) include at least one of the organic aluminum oxy compounds represented by the following general formula.

Embedded image (Wherein R ¹⁰ -R ¹⁴ may be the same or different, and
A hydrocarbon group from 1 to C8, and n represents an integer from 1 to 50. )

Representative examples of the cation generator of the catalyst component (B) include an organic boron compound represented by the following general formula.

(BR ¹⁵ R ¹⁶ R ¹⁷ ) _n , A (BR ¹⁵ R ¹⁶ R ¹⁷ R ¹⁸ ) _n (where A is a cation. R ^{15 to} R ¹⁸ may be the same or different, (C represents a hydrocarbon group containing a halogenated aryl group of C1 to C14, an alkoxy group, or an allyloxy group, and n represents an integer of 1 to 4.)

Here, the cation A of the compound includes a quaternary amine, a quaternary ammonium salt, a carbocation or a metal cation having a valence of +1 to 4, and specific examples thereof include pyridinium, 2,4-dinitro-N, N-diethylanilinium, p-nitroanilinium, 2,5-
Dichloroaniline p-nitro-N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, methyldiphenylammonium, N, N-diethylanilinium, 8-chloroquinolinium, trimethylammonium, tripropylammonium Examples include triethylammonium, tributylammonium, triphenylcarbocation, triphenylphosphonium, ammonium, sodium, lithium, potassium, cesium, calcium, magnesium and the like.

Specific examples of the hydrocarbon group of R ^{15 to} R ^{18 and} the hydrocarbon group portion of the alkoxy group and the allyloxy group include acetylacetonato, isopropyl, phenyl,
Benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4
6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, o-isopropoxyphenyl, pentafluorophenylpentafluorobenzyl, tetrafluorophenyl, tetrafluorotolyl and the like.

On the other hand, examples of the alkyl aluminum compound of the catalyst component (D) include organic aluminum compounds such as alkyl aluminum. Specific compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum hydride , Tri (2-ethylhexyl) aluminum, (2-ethylhexyl)
Aluminum dichloride and the like can be mentioned.

In addition to these, sodium aluminum hydride, potassium aluminum hydride, diisobutyl sodium aluminum hydride, tri (t)
-Butoxy) A hydride containing two or more metals such as aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride and triethyl lithium aluminum hydride may be used. Preferred among these compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dimethylaluminum chloride,
Examples thereof include methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, and diisobutylaluminum hydride. Further, a complex synthesized by preliminarily reacting the organic alkali metal compound and the organic aluminum compound, a complex (art complex) synthesized by preliminarily reacting, and the like are also included.

Specific examples of the alkyl alkali metal and / or alkyl alkaline earth metal compounds of the catalyst component (E) include organic lithium compounds, organic sodium compounds, organic potassium compounds, organic zinc compounds, organic magnesium compounds, and organic magnesium compounds. Examples thereof include an aluminum compound and an organic calcium compound, and they can be used alone or in combination with two or more (A).

Specific examples of the Li-containing compound include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, t-butyllithium, n-pentyllithium and n-pentyllithium. -Hexyllithium, phenyllithium, cyclopentadienyllithium, m-
Tolyl lithium, p-tolyl lithium, xylyl lithium, dimethylamino lithium, diethylamino lithium, methoxy lithium, ethoxy lithium, n-propoxy lithium, isopropoxy lithium, n-butoxy lithium, sec-butoxy lithium, t-butoxy lithium, pentyl Oxylithium, hexyloxylithium, heptyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, 4-methylbenzyloxylithium, and the like.

Further, organic silicon lithium compounds such as trimethylsilyllithium, diethylmethylsilyllithium, dimethylethylsilyllithium, triethylsilyllithium, and triphenylsilyllithium may be used. Containing Na
Specific examples of the compound include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium, isobutyl sodium, t-butyl sodium,
n-pentyl sodium, n-hexyl sodium, phenyl sodium, cyclopentadienyl sodium,
Examples thereof include sodium m-tolyl, sodium p-tolyl, sodium xylyl, and sodium naphthalene.

Specific examples of the K-containing compound include methyl potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, isobutyl potassium, t-butyl potassium,
Examples include n-pentyl potassium, n-hexyl potassium, triphenylmethyl potassium, phenyl potassium, phenylethyl potassium, cyclopentadienyl potassium, m-tolyl potassium, p-tolyl potassium, xylyl potassium, potassium naphthalene and the like.

Examples of the Zn-containing compound include diethyl zinc, bis (η ⁵ -cyclopentadienyl) zinc, diphenyl zinc and the like. Examples of the Mg-containing compound include dimethyl magnesium, diethyl magnesium, dibutyl magnesium and ethyl butyl magnesium. , Methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride, t-butyl magnesium chloride, t-butyl magnesium bromide and the like.

Other than these, alkali (earth) metal hydrides such as lithium hydride, potassium hydride, sodium hydride and calcium hydride;
Sodium aluminum hydride, potassium aluminum hydride, diisobutyl sodium aluminum hydride, tri (t-butoxy) aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride, triethyl lithium aluminum hydride, etc. A hydride containing more than one kind of metal may be used. Further, a complex synthesized by preliminarily reacting the organic alkali metal compound and the organic aluminum compound, a complex (art complex) synthesized by preliminarily reacting the organic alkali metal compound and the organic magnesium compound, and the like are also included. It is.

Catalysts suitable for use in the present invention include the transition metal compound (A) and the alkyl aluminum oxy compound (B), or the cation generator (A) and the component (C). Or a cation generator as component (A), component (B) and component (C), or an alkyl aluminum compound as component (A), component (B) and component (D), or component (A) and (D Component (A), the component (A), the component (B) and the component (E), the alkyl alkali metal and / or the alkyl alkaline earth metal, or the component (A) and the component (B). Component (C) and component (D), or component (A), component (B), component (C) and component (E), component (A), component (B), component (D) and component (E) , The components (A) and (E) There are combined saw, and the catalyst component (A) in combination of the above (B) (C) (D)
It is produced by combining any of the components (E) in any order and in any suitable manner.

The preferred catalyst composition ratio of the components (A) and (B) is (A) :( B) = 1: 0.01 to 1: 100.
00, a preferable catalyst composition ratio of the catalyst (A) component and the component (C) is (A) :( C) = 1: 0.01 to 1: 100, and a preferable catalyst composition of the catalyst (A) component and the component (D). The ratio is (A) :( D) = 1: 0.01 to 1: 1000, and the preferred catalyst composition ratio between the catalyst (A) and the component (E) is (A) :( E) = 1: 0.01 to 1: 100. The catalyst composition may be prepared in advance by mixing in a suitable solvent under an atmosphere of an inert gas such as nitrogen or argon, or each of (A), (B), (C), (D) and (E) May be separately poured into a reactor where a monomer coexists, and then prepared in the reactor. Suitable solvents for preparing the catalyst include hydrocarbon solvents such as alkane such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene. In addition, it is preferable to remove water and the like in these solvents in the pretreatment. The optimum temperature for preparing the catalyst composition is -20 ° C to 150 ° C.

The polymerization method of the present invention can be carried out in the presence of a monomer and a catalyst under reduced pressure, atmospheric pressure, or pressure.
Any of bulk, solution, and slurry methods can be used. The preferred temperature range for carrying out the polymerization is -30
C. to 260.degree. C., preferably 0 to 200.degree. In the polymerization, the polymerization may be performed in an atmosphere of an inert gas such as nitrogen or argon, or may be performed in an atmosphere of ethylene. In addition, ethylene and / or propylene and / or butylene may be mixed with the above inert gas. It may be in a mixed atmosphere. Further, hydrogen may be allowed to coexist in addition to the above gas for controlling the molecular weight. Further, the catalyst component may be supported on a suitable carrier such as alumina, magnesium chloride or silica. If desired, a solvent can be used in the polymerization.

Suitable solvents for use in the polymerization include alkane and other hydrocarbon solvents such as hexane and cyclohexane, and toluene, benzene, ethylbenzene, and the like.
And other aromatic solvents. As the monomer used for the polymerization, ethylene and styrene are most preferable.However, if necessary, other olefin compounds such as propylene and butylene, and aromatic vinyl compounds such as α-methylstyrene and diphenylethylene may coexist. Can be done.
The preferred amount of the catalyst in this polymerization is [(weight of the produced polymer)
Kg] / [catalyst (A) component 1 mol] = 50 kg / 1 m
ol to 100,000,000 kg / 1 mol.

As a method of separating the polymer after polymerization in the present invention, for example, a method of adding a polar solvent such as acetone or a poor solvent such as alcohol mixed with an acid or an alkali to a polymerization solution to precipitate and recover the polymer is used. A method in which the reaction solution is poured into boiling water with stirring and then distilled and recovered together with the solvent, or a method in which the reaction solution is directly heated to distill the solvent. First, the polymerization catalyst of the present invention is easily synthesized, has excellent heat resistance, and exhibits high activity in a polymerization reaction in a wide temperature range. Second, storage stability and activity stability are extremely excellent. Therefore, the activity of the catalyst almost maintains the initial polymerization activity even after several months.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. The catalyst components used in carrying out the examples and comparative examples are shown below. [Catalyst (A) Component] (Synthesis Example 1) Synthesis of 2,3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl-N-7-azaindole 2,3,4,5- Synthesis of tetramethyl-2,4-cyclopentadienyldimethylsilyl chloride 13.2 mmol of 1,2,4,5-tetramethyl-1,3-cyclopentadiene was placed in a 200 ml Schlenk tube and purged with nitrogen. 80 ml of dehydrated tetrahydrofuran was added and cooled to -40 ° C. While stirring, 13.2 mmol of n-butyllithium was slowly added dropwise. After the solution became cloudy, the mixture was stirred at 0 ° C. for 2 hours. 15 mmol of dimethyldichlorosilane was dripped at once, and the mixture was stirred overnight. After the reaction, the solvent and excess dimethyldichlorosilane were distilled off under reduced pressure to obtain a yellow liquid. This was purified by distillation under reduced pressure and used for the next reaction.

Synthesis of 2,3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl-N-7-azaindole 13.2 mmol of 7-azaindole was dissolved in 40 ml of dehydrated tetrahydrofuran at -40 ° C. Cooled down. n-
13.2 mmol of butyllithium was added, and the mixture was stirred for 1 hour.
It returned to room temperature and stirred overnight. After cooling to 0 ° C., a solution of 2,3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl chloride previously synthesized in tetrahydrofuran (THF) was added dropwise. After stirring for 1 hour, the mixture was returned to room temperature and stirred overnight. After the reaction, the residue was dried under reduced pressure, and dehydrated toluene 40 m
1 was added and the insoluble matter was filtered off. The liquid layer was dried under reduced pressure. 3.2 g of a pale yellow oil was obtained (81.8% yield).

Synthesis of Ti (thf) ₃ Cl ₃ A methylene chloride-THF solution containing 20 mmol of TiCl ₃ was placed in a Schlenk tube purged with nitrogen, methylene chloride was distilled off, and 60 ml of THF was added.
The mixture was heated to reflux for 0 hour, and the formed light blue complex was separated by filtration and washed twice with dehydrated pentane (yield 70%).

Synthesis of [(N-7-azaindolyl) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride 2,3,4,5-tetramethyl-2 , 4-Cyclopentadienyldimethylsilyl-N-7-azaindole 5m
mol was dissolved in 20 ml of dehydrated tetrahydrofuran.
After cooling to 5 ° C., 5 mmol of n-butyllithium was added and the mixture was stirred for 2 hours. Subsequently, it was added to a THF solution of 5 mmol of Ti (thf) ₃ Cl _{3 and} stirred overnight. After evaporating to dryness under reduced pressure, 10 ml of dehydrated toluene was added thereto, and the insoluble matter was separated by filtration.

Synthesis Example 2 Synthesis of 2,3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl-N, N-diethylamine 13.2 mmol of diethylamine was dissolved in 40 ml of dehydrated tetrahydrofuran to obtain -40. Cooled to ° C. 13.2 mmol of n-butyllithium was added, and the mixture was stirred for 1 hour, returned to room temperature and stirred overnight. Cooled to 0 ° C.,
A THF solution of 3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl chloride was added dropwise. After stirring for 1 hour, the mixture was returned to room temperature and stirred overnight. After the reaction, the mixture was dried under reduced pressure, 40 ml of dehydrated toluene was added, and the insoluble matter was filtered off.
The liquid layer was dried under reduced pressure to obtain a pale yellow oil.

Synthesis of [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride 2,3,4,5-tetramethyl-2 , 4-Cyclopentadienyldimethylsilyl-N, N-diethylamine 5m
mol was dissolved in 20 ml of dehydrated tetrahydrofuran.
After cooling to 5 ° C., 5 mmol of n-butyllithium was added and the mixture was stirred for 2 hours. Subsequently, it was added to a THF solution of 5 mmol of Ti (thf) ₃ Cl _{3 and} stirred overnight. After evaporating to dryness under reduced pressure, 10 ml of dehydrated toluene was added thereto, and the insoluble matter was separated by filtration.

(Synthesis Example 3) Synthesis of 2,3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl-N, N-dimethylamine A THF solution of dimethylamine (13.2 mmol) was dehydrated in tetrahydrofuran. Dissolved in 40 ml and cooled to -40 ° C. 13.2 mmol of n-butyllithium was added and 1
The mixture was stirred for an hour, returned to room temperature, and stirred overnight. After cooling to 0 ° C., THF of 2,3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl chloride synthesized earlier
The solution was added dropwise. After stirring for 1 hour, the mixture was returned to room temperature and stirred overnight. After the reaction, the reaction mixture was dried under reduced pressure, 40 ml of dehydrated toluene was added thereto, and the insoluble matter was separated by filtration. The liquid layer was dried under reduced pressure to obtain a pale yellow oil.

Synthesis of [(N, N-dimethylamino) dimethylsilyl, 2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride 2,3,4,5-tetramethyl- 2,4-cyclopentadienyldimethylsilyl-N, N-dimethylamine 5m
mol was dissolved in 20 ml of dehydrated tetrahydrofuran.
After cooling to 5 ° C., 5 mmol of n-butyllithium was added and the mixture was stirred for 2 hours. Subsequently, it was added to a THF solution of 5 mmol of Ti (thf) ₃ Cl _{3 and} stirred overnight. After evaporating to dryness under reduced pressure, 10 ml of dehydrated toluene was added thereto, and the insoluble matter was separated by filtration.

Synthesis Example 4 (Nt-butylamino) dimethylsilyl-2,3
Synthesis of 4,5-tetramethyl 2,4-cyclopentadiene 8.2 mmol of t-butylamine was dissolved in 40 ml of dehydrated tetrahydrofuran and cooled to -40 ° C. 8.2 mmol of n-butyllithium was added, and the mixture was stirred for 1 hour, returned to room temperature, and stirred overnight. Cooled to 0 ° C.,
A THF solution of 3,4,5-tetramethyl-2,4-cyclopentadienyldimethylsilyl chloride was added dropwise. After stirring for 1 hour, the mixture was returned to room temperature and stirred overnight. After the reaction, the residue was dried under reduced pressure, 40 ml of dehydrated toluene was added, and the insoluble matter was filtered off. The liquid layer was dried under reduced pressure. A pale yellow oil was obtained.

Synthesis of Ti (thf) ₃ Cl ₃ A methylene chloride-THF solution containing 20 mmol of TiCl ₃ was placed in a Schlenk tube purged with nitrogen, methylene chloride was distilled off, and 60 ml of THF was added. Attach Jim Roth 2
The mixture was heated to reflux for 0 hour, and the formed light blue complex was separated by filtration and washed twice with dehydrated pentane (yield 70%).

Synthesis of [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl2,4-cyclopentadienyl] titanium dichloride (Nt-butylamino) dimethylsilyl-2,3
4,5-tetramethyl 2,4-cyclopentadiene
1 mmol was dissolved in 20 ml of dehydrated toluene,
And cooled. 10.2 mmol of n-BuLi was added and stirred for 2 hours. This was cooled to −78 ° C. in advance and dispersed in 20 ml of toluene, Ti (thf) ₃ Cl _3.
Added. After 15 minutes, 6 mmol of AgCl was added and the mixture was stirred overnight. This was dried under reduced pressure and dried methylene chloride (60 ml).
Was added. After filtration, the liquid layer was dried under reduced pressure. Hexane 20m
1 to obtain the desired product.

[0053]

Example 1 After replacing the inside of the apparatus with nitrogen, a reactor (2 l autoclave) was connected, and the inside of the reactor was replaced with nitrogen. Toluene was passed through a purification tower, sampled in a measuring tube in an amount of 280 ml, and then degassed under reduced pressure for 5 minutes. The inside of the reactor was depressurized and the measuring tube was pressurized, and 20 mmol of methylalumoxane (MMAO) was poured into the catalyst tank as the component (B), and the mixture was transferred to the reactor with 280 ml of toluene in the measuring tube. Similarly, after 920 ml of styrene was sampled and deaerated, 740 ml was transferred into the reactor. The reactor was heated to 90 ° C., and then [(N-7-azaindolyl) dimethylsilyl-2,
3,4,5-Tetramethyl-2,4-cyclopentadienyl] titanium dichloride 20 μmol toluene solution was poured into the catalyst tank, and styrene 18
Transferred at 0 ml. 10 kg / ethylene in reactor
After pressurizing to ² cm ² , the ethylene supply line was stopped and stirring was started. Since the gauge pressure was lowered with the polymerization, ethylene was appropriately supplied during the polymerization, and the polymerization was carried out for 60 minutes while maintaining the predetermined pressure. After the polymerization, the polymer solution was treated in methanolic hydrochloric acid to recover the polymer. Polymer yield 51 g, NM
From the R measurement, the styrene content in the polymer was 33% by weight.

[0054]

Example 2 After replacing the inside of the apparatus with nitrogen, a reactor (2 l autoclave) was connected, and the inside of the catalyst tank and the reactor was replaced with nitrogen. Toluene is passed through the purification tower and 280
After sampling ml, the solution was degassed under reduced pressure for 5 minutes. The pressure in the reactor is reduced and the catalyst tank contains M as component (B).
MAO was transferred to a 20 mmol implantation reactor. ,
280 ml of toluene in the measuring tube was transferred to the reactor.
Similarly, 920 ml of styrene was sampled, deaerated, and then transferred into the reactor. 90 ° C reactor
Then, a toluene solution of [(N-7-azaindolyl) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride as the component (A) was used as a catalyst. It was driven into the tank and transferred to the reactor. 6 inside the reactor with ethylene
After pressurizing to kg / cm ² , the ethylene supply line was stopped and stirring was started. Since the gauge pressure was lowered with the polymerization, ethylene was appropriately supplied during the polymerization, and the polymerization was carried out for 60 minutes while maintaining the predetermined pressure. After the polymerization, the polymer solution was treated in methanolic hydrochloric acid to recover the polymer. Polymer yield 49
g, NMR measurement shows that the styrene content in the polymer is 43 w
t%.

[0055]

Example 3 After replacing the inside of the apparatus with nitrogen, a reactor (2 l autoclave) was connected, and the inside of the reactor was replaced with nitrogen. Toluene was passed through a purification tower, sampled in a measuring tube in an amount of 600 ml, and then degassed under reduced pressure for 5 minutes. The reactor was depressurized and the measuring tube was pressurized, and [(N-7-azaindolyl) dimethylsilyl-2,
3,4,5-Tetramethyl-2,4-cyclopentadienyl] titanium dichloride in 20 μmol toluene solution, and a mixture of 20 mmol of MMAO as the component (B) in advance were injected, and toluene 2
Transferred to the reactor at 80 ml. Similarly, add styrene to 60
After sampling 0 ml and performing a deaeration operation, it was transferred into the reactor. After heating the reactor to 90 ° C. and pressurizing the interior of the reactor with ethylene to 10 kg / cm ² , the ethylene supply line was stopped and stirring was started. Since the gauge pressure was lowered with the polymerization, ethylene was appropriately supplied during the polymerization, and the polymerization was carried out for 60 minutes while maintaining the predetermined pressure. After the polymerization, the polymer solution was treated in methanolic hydrochloric acid to recover the polymer. The polymer yield was 46 g, and the styrene content in the polymer was 12 wt% based on NMR measurement.

[0056]

Example 4 Example 4 was repeated except that a mixture of the components (A) and (B) was prepared in advance and stored for one month. The polymer yield was 45 g, and the styrene content in the polymer was 30 wt% based on NMR measurement.

[0057]

Example 5 The same procedure as in Example 2 was carried out except that a mixture of the components (A) and (B) prepared in advance and stored for one month was used. The polymer yield was 45 g, and the styrene content in the polymer was 39 wt% based on NMR measurement.

[0058]

Example 6 The same procedure as in Example 3 was carried out except that a mixture of the components (A) and (B) prepared in advance and stored for one month was used. The polymer yield was 43 g, and the styrene content in the polymer was 12 wt% based on NMR measurement.

[0059]

Example 7 Example 7 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). This was performed in the same manner as in Example 1. The polymer yield was 41 g, and the styrene content in the polymer was 17 wt% based on NMR measurement.

[0060]

Example 8 Example 1 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in a similar manner to 2. The polymer yield was 52 g, and the styrene content in the polymer was 19 wt% based on NMR measurement.

[0061]

Example 9 Example 9 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in a similar manner to 3. The polymer yield was 46 g, and the styrene content in the polymer was 8 wt% based on NMR measurement.

[0062]

Example 10 Example 10 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). This was performed in the same manner as in Example 4.
The polymer yield was 39 g, and the styrene content in the polymer was 31 wt% based on NMR measurement.

[0063]

Example 11 The procedure was carried out except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium tridilide was used as the component (A). Performed in the same manner as in Example 5.
The polymer yield was 44 g, and the styrene content in the polymer was 37 wt% based on NMR measurement.

[0064]

Example 12 Example 12 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). 6 was performed in the same manner.
The polymer yield was 46 g, and the styrene content in the polymer was 10 wt% based on NMR measurement.

[0065]

Example 13 Example 13 was repeated except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 1.
The polymer yield was 38 g, and the styrene content in the polymer was 31 wt% based on NMR measurement.

[0066]

Example 14 Example 14 was carried out except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 2.
The polymer yield was 34 g, and the styrene content in the polymer was 38 wt% based on NMR measurement.

[0067]

Example 15 Except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium trichloride was used as the component (A) This was performed in the same manner as in Example 3. The polymer yield was 41 g, and the styrene content in the polymer was 12 wt% based on NMR measurement.

[0068]

Example 16 Example 16 was repeated except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 4.
The polymer yield was 35 g, and the styrene content in the polymer was 26 wt% based on NMR measurement.

[0069]

Example 17 The procedure was carried out except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 5.
The polymer yield was 35 g, and the styrene content in the polymer was 40 wt% based on NMR measurement.

[0070]

Example 18: [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium trichloride was used as the component (A). This was performed in the same manner as in Example 6. The polymer yield was 34 g, and the styrene content in the polymer was 11 wt% based on NMR measurement.

[0071]

Example 19 After replacing the inside of the apparatus with nitrogen, a reactor (2 l autoclave) was connected, and the inside of the reactor was replaced with nitrogen.
Toluene was passed through a purification tower, sampled in a measuring tube in an amount of 600 ml, and then degassed under reduced pressure for 5 minutes. The inside of the reactor was depressurized and the measuring tube was pressurized. 10 mmol of MMAO as the component (B) and 10 mmol of trimethylaluminum as the component (D) were introduced into the catalyst tank, and were transferred to the reactor with 280 ml of toluene in the measuring tube. Similarly, after sampling 600 ml of styrene and performing degassing operation,
Transferred into the reactor. The reactor was heated to 90 ° C., and then [(N-7-azaindolyl) dimethylsilyl-2,3,4,5-tetramethyl-2,4 as component (A)
-Cyclopentadienyl] titanium dichloride 20
A μmol toluene solution was poured into the catalyst tank, and was transferred with 180 ml of styrene in a measuring tube. After pressurizing the reactor with ethylene to 10 kg / cm ² , the ethylene supply line was stopped, and stirring was started. Since the gauge pressure was lowered with the polymerization, ethylene was appropriately supplied during the polymerization, and the polymerization was carried out for 60 minutes while maintaining the predetermined pressure. After the polymerization, the polymer solution was treated in methanolic hydrochloric acid to recover the polymer. The polymer yield was 32 g, and the styrene content in the polymer was 41 wt% based on NMR measurement.

[0072]

Embodiment 20 After replacing the inside of the apparatus with nitrogen, a reactor (2 l autoclave) was connected, and the inside of the reactor was replaced with nitrogen.
Toluene was passed through a purification tower, sampled in a measuring tube in an amount of 600 ml, and then degassed under reduced pressure for 5 minutes. The inside of the reactor was depressurized and the measuring tube was pressurized. 15 mmol of MMAO as the component (B) and 5 mmol of dibutylmagnesium as the component (E) were charged into the catalyst tank, and were transferred to the reactor with 280 ml of toluene in the measuring tube. Similarly, 600 ml of styrene was sampled, deaerated, and then transferred into the reactor. The reactor was heated to 90 ° C., and then [(N-7-azaindolyl) dimethylsilyl, 2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride 20 μm as component (A)
ol of a toluene solution was poured into a catalyst tank, and was transferred by 180 ml of styrene in a measuring tube. After pressurizing the reactor with ethylene to 10 kg / cm ² , the ethylene supply line was stopped, and stirring was started. Since the gauge pressure was lowered with the polymerization, ethylene was appropriately supplied during the polymerization, and the polymerization was carried out for 60 minutes while maintaining the predetermined pressure. After the polymerization, the polymer solution was treated in methanolic hydrochloric acid to recover the polymer. The polymer yield was 33 g, and the styrene content in the polymer was 38 wt% based on NMR measurement.

[0073]

Example 21 After the inside of the apparatus was replaced with nitrogen, a reactor (2 l autoclave) was connected, and the inside of the reactor was replaced with nitrogen.
Toluene was passed through a purification tower, sampled in a measuring tube in an amount of 600 ml, and then degassed under reduced pressure for 5 minutes. The pressure in the reactor was reduced and the pressure in the measuring tube was increased. 0.2 mmol of (C ₆ F ₅ ) ₃ B was poured into the catalyst tank as the component (C), and the solution was transferred to the reactor with 280 ml of toluene in the measuring tube. Similarly, 600 ml of styrene was sampled, deaerated, and then transferred into the reactor. The reactor was heated to 90 ° C., and then [(N-7-azaindolyl) dimethylsilyl-2,3,4,5-tetramethyl-
A toluene solution of 20 μmol of [2,4-cyclopentadienyl] titanium dichloride was poured into the catalyst tank, and was transferred with 180 ml of styrene in a measuring tube. After pressurizing the reactor with ethylene to 10 kg / cm ² , the ethylene supply line was stopped, and stirring was started. Since the gauge pressure was lowered with the polymerization, ethylene was appropriately supplied during the polymerization, and the polymerization was carried out for 60 minutes while maintaining the predetermined pressure. After the polymerization, the polymer solution was treated in methanolic hydrochloric acid to recover the polymer.
The polymer yield was 31 g, and the styrene content in the polymer was 36 wt% based on NMR measurement.

[0074]

Example 22 Example except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in a manner similar to 19. The polymer yield was 31 g, and the styrene content in the polymer was 10 wt% based on NMR measurement.

[0075]

Example 23 Example 23 was repeated except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 20. The polymer yield was 32 g, and the styrene content in the polymer was 34 wt% based on NMR measurement.

[0076]

Example 24 Example 24 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). This was performed in the same manner as in Example 21. The polymer yield was 30 g, and the styrene content in the polymer was 38 wt% based on NMR measurement.

[0077]

Example 25 The procedure was carried out except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 19. The polymer yield was 35 g, and the styrene content in the polymer was 28 wt% based on NMR measurement.

[0078]

Example 26 Example 26 was repeated except that [(N, N-diethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). 20 was performed in the same manner. The polymer yield was 34 g, and the styrene content in the polymer was 34 wt% based on NMR measurement.

[0079]

Example 27 Example 27 was repeated except that [(N, N-dimethylamino) dimethylsilyl-2,3,4,5-tetramethyl-2,4-cyclopentadienyl] titanium dichloride was used as the component (A). Performed in the same manner as in Example 21. The polymer yield was 23 g, and the styrene content in the polymer was 26 wt% based on NMR measurement.

[0080]

Comparative Example 1 [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl-
[2,4-Cyclopentadienyl] titanium dichloride was used in the same manner as in Example 1. The polymer yield was 32 g, and the styrene content in the polymer was 14 wt% based on NMR measurement.

[0081]

Comparative Example 2 [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl-
[2,4-Cyclopentadienyl] titanium dichloride was used in the same manner as in Example 2 except that titanium dichloride was used. The polymer yield was 34 g, and the styrene content in the polymer was 21 wt% based on NMR measurement.

[0082]

Comparative Example 3 [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl-
[2,4-cyclopentadienyl] titanium dichloride was used in the same manner as in Example 4. The polymer yield was 17 g, and the styrene content in the polymer was 14 wt% based on NMR measurement.

[0083]

Comparative Example 4 [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl-
[2,4-Cyclopentadienyl] titanium dichloride was used in the same manner as in Example 5, except that titanium dichloride was used. The polymer yield was 12 g, and the styrene content in the polymer was 21 wt% based on NMR measurement.

[0084]

Comparative Example 5 [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl-
[2,4-Cyclopentadienyl] titanium dichloride was used in the same manner as in Example 6 except that titanium dichloride was used. The polymer yield was 12 g, and the styrene content in the polymer was 21 wt% based on NMR measurement.

[0085]

Comparative Example 6 [(Nt-butylamido) dimethylsilyl-2,3,4,5-tetramethyl-
[2,4-Cyclopentadienyl] titanium dichloride was used in the same manner as in Example 3. The polymer yield was 24 g, and the styrene content in the polymer was 10 wt% based on NMR measurement.

[0086]

The polymerization catalyst of the present invention has excellent heat resistance of the catalyst, exhibits high activity in a polymerization reaction in a wide temperature range, and has extremely excellent storage stability and activity stability. Therefore, the activity of the catalyst almost maintains the initial polymerization activity even after several months.

Claims (5)

[Claims] 1. A polymerization catalyst, wherein the catalyst (A) component contains a complex represented by the following general formula (1). Embedded image (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. ) 2. A polymerization catalyst comprising a catalyst component (A) containing a complex represented by the following general formula (1) and a component (B) and / or a component (C). (A) (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. (B) Alkyl aluminum oxy compound (C) Cation generator 3. A polymerization catalyst comprising a catalyst (A) containing a complex represented by the following general formula (1) and a component (B) and / or a component (C) and / or a component (D). . (A) (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. (B) alkyl aluminum oxy compound (C) cation generator (D) alkyl aluminum compound 4. A catalyst comprising a complex represented by the following general formula (1): component (A) and component (B) and / or component (C) and / or component (D) and / or component (E). A polymerization catalyst characterized by the above-mentioned. (A) (Wherein, M is a transition metal of Group 4 and the 5-membered ring is a cyclopentadienyl group or a substituted cyclopentadienyl group, which is π-bonded to M by a cyclopentadienyl group η ^5. R ^{1 to} R ⁴ May be the same or different and may be hydrogen or C1
-C12 alkyl group, alkenyl group, alkoxy group,
Any two or three of the aryl group and the allyloxy group may be bonded to each other to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. Y
Is a carbon or Si or Ge element, and Z is any one of N, P, S, and O elements and has an interaction with a transition metal element by an unshared electron pair, but does not form a σ bond. X ¹ , X ² , R ^{5 to} R ⁷ may be the same or different, and each represents hydrogen or a C1 to C12 alkyl group;
It consists of an alkoxy group, an aryl group, an allyloxy group, and a halogen. m is an integer of 1 to 3, and n is a number corresponding to the valence -1 of the heteroatom bonded by an integer of 1 to 3. (B) alkyl aluminum oxy compound (C) cation generator (D) alkyl aluminum compound (E) alkyl alkali metal and / or alkyl alkaline earth metal compound 5. Ethylene and styrene, wherein the copolymer polymerized with the polymerization catalyst according to claim 1 contains 98.6 to 53 mol% of ethylene and 1.4 to 47 mol% of styrene. A method for producing a copolymer, characterized in that the copolymer is a pseudo-random copolymer.