JPH11199622A - Polymerization catalyst for copolymer and production of copolymer using the same catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst capable of being more simply synthesized in using industrially and expressing high reproducibility in long range preservation stability and activity by combining tetravalent complex of a group IV metal with a metal compound or a cation generating agent each having a specific structure. SOLUTION: This polymerization catalyst for copolymers contains (A) a complex expressed by the formula [M is a transition metal of the group IV; the 5 membered ring is a (substituted) cyclopentadienyl; R<1> to R<5> are each H, a 1-12C alkyl, alkenyl, alkoxy or the like X, Y and Z are each H, a 1-12C alkyl, alkoxy or the like and at least one of them is a dicarbonyl ligand having a structure of formula II (R<6> and R<7> are each H, a 1-12C alkyl, alkenyl or the like)], preferably (B) an alkylaluminumoxy compound and/or (C) a cation- generating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel complex catalyst 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, JP-A-3-163088 and JP-A-Hei.
A metal coordination complex having a constrained geometry of Group 4 or Group 3 such as -70223 is known as a catalyst system having high activity and excellent copolymerizability. However, these complex catalyst systems have a constrained geometric shape, so it is difficult to synthesize from tetravalent transition metal compounds, it takes a lot of time to synthesize the complex, and high purity complex cannot be obtained, resulting in high cost. There was a problem of becoming. In addition, there is a problem that the long-term storage stability and reproducibility of the activity of the complex are not sufficient, and there is a problem in industrial use.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to find a catalyst system which can be synthesized more easily on an industrial scale and has a long-term storage stability and a high reproducibility of the activity.

[0004]

According to the present invention, a group 4 tetravalent complex having a specific structure is easier to synthesize than a conventional complex, and (A) a group 4 tetravalent complex having a specific structure is used. It is based on the surprising fact that the combination with a metal compound having the structure of ## STR1 ## or a cation generator has a long-term storage stability and is far superior in terms of reproducibility of polymerization activity as compared with the conventional complex catalyst system. It is a thing.
That is, the present invention provides [1] a polymerization catalyst, wherein the catalyst (A) component contains a complex represented by the following general formula (1):

[0005]

Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). )

[0006]

Embedded image (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. )

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

Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). )

[0008]

Embedded image (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. (B) Alkyl aluminum oxy compound (C) Cation generator

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

Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). )

[0010]

Embedded image (However, R ⁶ and R ⁷ may be the same or different,
It consists of a C1-C12 alkyl group, alkenyl group, alkoxy group, aryl group, allyloxy group, alkylamide group, and arylamide group. (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 (C)
A polymerization catalyst comprising a component and / or a component (D) and / or a component (E)

Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). )

[0012]

Embedded image (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. (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 polymerization catalyst of the above [1] to [4] The copolymer being polymerized is 98.6-53 mol% of ethylene and 1.4-4
The present invention relates to a method for producing a copolymer, which is a pseudo-random copolymer of ethylene and styrene containing 7 mol% of styrene.

As a catalyst for copolymerizing ethylene and a vinyl aromatic monomer, JP-A-3-163088 and JP-A-7-16088.
There are metal coordination complexes having a constrained geometry such as 70223, but since these complex catalyst systems have a constrained geometry, it is difficult to synthesize from tetravalent transition metal compounds, and it takes time to synthesize the complex. However, there is a problem in that a complex having high purity cannot be obtained, resulting in an increase in cost. In addition, there is a problem that the long-term storage stability and reproducibility of the activity of the complex are not sufficient, and for industrial use,
A complex which has a copolymerization activity equal to or higher than that of the above complex, is more easily synthesized, and is easier to handle has been 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 easy to synthesize, and the stability of the complex is improved. (A) and (B) a combination of an aluminum oxy compound and / or (C) a cation generator, and (A) and (B) and / or (C) further (D) And / or a system in which the component (E) is combined has excellent copolymerization activity, has a wide polymerization temperature range, has a small decrease in activity due to the polymerization temperature, and has high activity reproducibility, and has completed the present invention. It is.

The 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 transition metal, Ti or Z
r or Hf. The 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl group is an indenyl group,
It also includes a fluorenyl group and the like. M and the substituted cyclopentadienyl group are π-bonded at η ⁵ , and the carbons of the 5-membered ring are 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. X, Y, and Z may be the same or different, each consisting of hydrogen or a C1 to C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2).

[0017]

Embedded image (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. In the dicarbonyl compound represented by the general formula (2), the methylene moiety between the two carbonyl groups is usually deprotonated to form a monovalent anion when forming a bond with the transition metal M. And is coordinated to M in the form of a resonance structure.

In the general formula (1), the alkyl, aryl and alkoxy groups of R ^{1 to} R ⁵ , the alkyl and aryl portions of the allyloxy group, and the general formula (2)
Specific examples of the alkyl group, aryl group, and alkoxy group, the alkyl and aryl portions of the allyloxy group, and the alkyl and aryl portions of the alkylamide group and the arylamide group include hydrogen, methyl, ethyl, propyl, isopropyl, and 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,
-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-dimethylhexyl,

1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 3,4-dimethylhexyl
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-ethylmethylpentyl, 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-dimethyl Cyclohexyl 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, -Methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl1, 1-dimethylheptyl,
2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 5,5-dimethylheptyl, 6,6-dimethylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, , 4-dimethylheptyl,

1,5-dimethylheptyl, 1,6-dimethylheptyl, 2,3-dimethylheptyl, 2,4-dimethylheptyl, 2,5-dimethylheptyl, 2,6-dimethylheptyl
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,

1,2,5-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-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-
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, , 6-dimethyloctyl, 2,7-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 3,7-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, mesityl, 2,6-dimethylphenyl, 2,4
6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl and o-isopropoxyphenyl.

The aluminum oxy compound of the catalyst component (B) includes at least one of the organic aluminum oxy compounds represented by the following general formula (3).

Embedded image (R ^{10 to} R ¹⁴ may be the same or different;
Hydrocarbon groups up to 8, n represents an integer from 1 to 50)

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

Embedded image (BR ¹⁵ R ¹⁶ R ¹⁷ ) _n A (BR ¹⁵ R ¹⁶ R ¹⁷ R ¹⁸ ) _n (A is a cation. R ^{15 to} R ¹⁸ may be the same or different; A hydrocarbon group containing a halogenated aryl group, an alkoxy group, an allyloxy group n is 1
Wherein the cation of compound A is 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, triethylammonium, tributylammonium, triphenylcarbocation, triphenylphosphonium, ammonium, sodium, lithium, potassium, cesium, calcium, magnesium, etc. Can be

Specific examples of the hydrocarbon group of R ^{15 to} R ^{18 and} the hydrocarbon group of the alkoxy group and the allyloxy group include allylacetonato, isopropyl, phenyl, benzyl, p-tolyl, m-tolyl and 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, 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) aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride, triethyl lithium aluminum aluminum A hydride containing two or more metals such as hydride may be used. Preferred among these compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dimethylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum hydride and the like. . 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 aluminum compounds. , An organic calcium compound, etc., but they can be used alone or in combination of two or more.

Specific examples of the Li-containing compound include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, t-butyllithium,
n-pentyllithium, n-hexyllithium, phenyllithium, cyclopentadienyllithium, m-tolyllithium, p-tolyllithium, xylyllithium,
Dimethylaminolithium, diethylaminolithium, methoxylithium, ethoxylithium, n-propoxylithium, isopropoxylithium, n-butoxylithium, sec-butoxylithium, t-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyl Oxylithium, 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-butyl sodium,
-Pentyl sodium, n-hexyl sodium, phenyl sodium, cyclopentadienyl sodium, m
-Sodium tolyl, p-tolyl sodium, sodium xylyl, sodium naphthalene and the like.

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, and n-butyl potassium.
-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 can be mentioned. Examples of the Zn-containing compound include diethyl zinc, bis (η5-cyclopentadienyl) zinc, diphenyl zinc and the like.
Compounds include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, 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 And bromide.

In addition to 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.

The catalyst suitable for use in the present invention is a transition metal compound as the component (A) and an alkylaluminum oxy compound as the component (B), or a cation generator as the components (A) and (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), component (A), component (B) and component (E), alkyl alkali metal or alkyl alkaline earth metal, or component (A), component (B) and component (C). ) Component and (D) component, or (A) component, (B) component, (C) component and (E) component,
(A) component, (B) component, (D) component, and (E) component,
There is a combination of the component (A) and the component (E). In the above combination, the catalyst (A) and the catalyst (B) (C) (D) (E)
It is made by combining any of the components in any order and in any suitable manner. A preferable catalyst composition ratio of the catalyst (A) component and the catalyst (B) component is (A) :( B) =
1: 0.01 to 1: 10000, and 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 ratio of the catalyst (A) component and the catalyst (D) component is (A) :( D) = 1: 0.0
The preferred catalyst composition ratio of the components (A) and (E) is (A) :( E) = 1: 0.01 to 1: 1,000.
100.

The preparation of the catalyst composition may be carried out in advance by mixing in a suitable solvent under an atmosphere of an inert gas such as nitrogen or argon, or (A), (B) or (C).
(D) (E) Each component may be separately poured into a reactor where a monomer coexists, and may be 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. Further, 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, in the presence of a monomer and a catalyst, reduced pressure,
Atmospheric pressure, pressurized condition, bulk, solution,
It can be performed by any method of slurry.

The preferred temperature range for carrying out the polymerization is-
The temperature is 30 ° C to 260 ° C, preferably 0 ° C to 200 ° C. 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. Also,
The catalyst component may be used by being 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 hydrocarbon solvents such as alkane such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene. 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. A suitable amount of the catalyst in the main polymerization is [(weight of polymer produced) Kg] / [1 mol of catalyst (A) component] = 50 kg / 1 mol to 1000
This is an amount giving about 0000 kg / 1 mol of polymer. As a method for separating the polymer after polymerization in the present invention, for example, a method of adding a polar solvent such as acetone or an alcohol mixed with an acid or an alkali to be a poor solvent to the polymerization solution to precipitate and recover the polymer, a reaction solution Into a boiling water under stirring and then distilling and recovering it with a solvent, or directly heating the reaction solution to distill off 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.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The catalyst components used in carrying out the examples and comparative examples are shown below. [Catalyst (A) Component] (Synthesis Example 1) Synthesis of Cp ^* Ti [CH (COOC ₂ H ₅ ) ₂ ] _n Cl _3-n 13.2 mmol of NaH was added to 30 ml of dehydrated THF, and the mixture was cooled to 0 ° C. 13.2 mmol of diethyl malonate was slowly added dropwise, followed by stirring for 2 hours. This is called Cp ^* T
A solution of 13.2 ml of iCl ₃ in 20 ml of THF was added dropwise and stirred overnight. After evaporating to dryness under reduced pressure, the residue was dissolved in dehydrated toluene. The soluble and insoluble components were separated by adding dehydrated hexane. From NMR, it was found that the soluble component was disubstituted and the insoluble component was monosubstituted.
Obtained various kinds of objects.

(Example 1) 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 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 was reduced and the pressure in the measuring tube was increased. In the catalyst tank, MMAO (methylaminoxan) was added as component (B).
0 mmol was injected, and the mixture was transferred to the reactor with 280 ml of toluene in a 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 Cp ^* Ti [CH (COOC ₂ H ₅ ) as component (A).
₂ ] A toluene solution of ₂₀ μmol of Cl _{2 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 polymerization,
The polymer solution was treated in methanolic hydrochloric acid to recover the polymer. The polymer yield was 52 g, and the styrene content in the polymer was 62 wt% based on NMR measurement.

Example 2 After the inside of the apparatus was replaced with nitrogen, a reactor (2 L autoclave) was connected, and the inside of the catalyst tank and 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. Reduce the pressure in the reactor and put it in the catalyst tank (B)
As a component, 20 mmol of MMAO was transferred into the reactor. Then, 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. The reactor was heated to 90 ° C. and then Cp ^* as component (A) ^.
Ti [CH (COOC ₂ H ₅ ) ₂ ] Cl _{2 20} μmol
Was poured into the catalyst tank and transferred to the reactor. After pressurizing the reactor with ethylene to 6 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 41 g, and the styrene content in the polymer was 63 wt% based on NMR measurement.

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 is passed through a purification tower, and 600
After sampling ml, the solution was degassed under reduced pressure for 5 minutes. The pressure in the reactor is reduced and the pressure in the measuring tube is increased. In the catalyst tank, Cp ^* Ti [CH (COOC ₂ H ₅ ) is used as the component (A).
₂ ] A toluene solution of ₂₀ μmol of Cl ₂ and a mixture obtained by previously mixing 20 mmol of MMAO as the component (B) were injected, and the mixture was transferred to the reactor with 280 ml of toluene in a measuring tube. Similarly, 600 ml of styrene was sampled, deaerated, and then transferred into the reactor. Heat the reactor to 90 ° C and fill the reactor with 10 kg of ethylene
After pressurizing to / 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 40 g, N
From the MR measurement, the styrene content in the polymer was 59% by weight.

(Example 4) The same procedure as in (Example 1) was carried out except that a mixture of the components (A) and (B) which had been prepared in advance and stored for one month was used. Polymer yield 41
g, styrene content in the polymer was 61 w
t%. (Example 5) (Example 2) except that a mixture of the components (A) and (B) prepared in advance and stored for one month was used.
Was performed in the same manner as described above. Polymer yield 39 g, NMR
From the measurement, the styrene content in the polymer was 60% by weight. (Example 6) Except for using a mixture of the components (A) and (B), which was prepared in advance and stored for one month (Example 3)
Was performed in the same manner as described above. Polymer yield 40 g, NMR
From the measurement, the styrene content in the polymer was 60% by weight. Example 7 Cp ^* Ti [CH (CO (CO)
OC ₂ H _{5) 2]} except for using ₂ Cl was carried out in the same manner as Example 1. The polymer yield was 37 g, and the styrene content in the polymer was 62 wt% based on NMR measurement.

(Embodiment 8) Cp ^* Ti as the component (A)
The procedure was the same as in Example 2 except that [CH (COOC ₂ H ₅ ) ₂ ] ₂ Cl was used. Polymer yield of 4
4 g, the styrene content in the polymer was 63 based on NMR measurement.
wt%. (Example 9) As the component (A), Cp ^* Ti [CH (CO
OC ₂ H _{5) 2]} except for using ₂ Cl was carried out in the same manner (Example 3). The polymer yield was 46 g, and the styrene content in the polymer was 59 wt% based on NMR measurement.

Example 10 Cp ^* T as the component (A)
The same procedure as in (Example 4) was performed except that i [CH (COOC ₂ H ₅ ) ₂ ] ₂ Cl was used. Polymer yield of 4
4 g, styrene content in the polymer was 64 by NMR measurement.
wt%. (Example 11) As the component (A), Cp ^* Ti [CH (C
OOC ₂ H ₅ ) ₂ ] ₂ Cl (Example 5)
Was performed in the same manner as described above. Polymer yield 43 g, NMR
From the measurement, the styrene content in the polymer was 59% by weight. (Example 12) As the component (A), Cp ^* Ti [CH (C
OOC ₂ H ₅ ) ₂ ] ₂ Cl (Example 6)
Was performed in the same manner as described above. Polymer yield 46 g, NMR
From the measurement, the styrene content in the polymer was 62% by weight.

Example 13 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 is passed through the purification tower and 60
After sampling 0 ml, the solution was degassed under reduced pressure for 5 minutes.
The reactor was depressurized, the measuring tube was pressurized, and 10 mmol of MMAO as the component (B) and 10 mmol of trimethylaluminum as the component (D) were poured into the catalyst tank.
It 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. 90 ° C reactor
And then Cp ^* Ti [CH as the component (A).
(COOC ₂ H ₅ ) ₂ ] Cl ₂ 20 mmol 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 33 g, NM
From the R measurement, the styrene content in the polymer was 63% by weight.

Example 14 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 is passed through the purification tower and 60
After sampling 0 ml, the solution was 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 Cp ^* Ti [CH (CO
OC ₂ H ₅ ) ₂ ] Cl _{2 20} μmol of a toluene solution was poured into a catalyst tank, and 180 ml of styrene in a measuring tube was poured.
Transported by 10 kg / cm ^{2 of} ethylene in the reactor
After pressurizing, 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 50 wt% based on NMR measurement.

Example 15 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 is passed through the purification tower and 60
After sampling 0 ml, the solution was 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 Cp ^* Ti as component (A).
A toluene solution of [CH (COOC ₂ H ₅ ) ₂ ] Cl ₂ ( ₂₀ μmol) was poured into the catalyst tank, and was transferred with 180 ml of styrene in a measuring tube. 10 reactors 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. 32 polymer yield
g, styrene content in the polymer was 69 w
t%.

(Example 16) Cp ^* T as the component (A)
The same procedure as in (Example 13) was performed except that i [CH (COOC ₂ H ₅ ) ₂ ] ₂ Cl was used. The polymer yield was 31 g, and the styrene content in the polymer was 5 based on NMR measurement.
It was 8 wt%. (Example 17) Cp ^* Ti [CH (C (C)
OOC ₂ H ₅ ) ₂ ] ₂ Cl (Example 1)
It carried out by the same method as 4). Polymer yield 32 g, N
From the MR measurement, the styrene content in the polymer was 59% by weight.

(Example 18) Cp ^* T as the component (A)
The same procedure was performed as in Example 15 except that i [CH (COOC ₂ H ₅ ) ₂ ] ₂ Cl was used. The polymer yield was 38 g, and the styrene content in the polymer was 5 based on NMR measurement.
It was 8 wt%. (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 31 g, and the styrene content in the polymer was 59 wt% based on NMR measurement.

(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). The polymer yield was 34 g, and the styrene content in the polymer was 21 wt% based on NMR measurement. (Comparative Example 3) [(Nt-butylamido) dimethylsilyl, 2,3,4,5-tetramethyl-
(2,4-cyclopentadienyl) titanium dichloride was used, except that (Example 4) was used.
The polymer yield was 17 g, and the styrene content in the polymer was 14 wt% based on NMR measurement.

(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). The polymer yield was 12 g, and the styrene content in the polymer was 21 wt% based on NMR measurement. (Comparative Example 5) [(Nt-butylamido) dimethylsilyl, 2,3,4,5-tetramethyl-
(2,4-cyclopentadienyl) titanium dichloride was used, except that (Example 6) was used.
The polymer yield was 12 g, and the styrene content in the polymer was 21 wt% based on NMR measurement. (Comparative Example 6) [(Nt-butylamido) dimethylsilyl, 2,3,4,5-tetramethyl-
(2,4-cyclopentadienyl) titanium dichloride was used, except that (Example 3) was used.
The polymer yield was 24 g, and the styrene content in the polymer was 10 wt% based on NMR measurement.

[0051]

The polymerization catalyst of the present invention is easy to synthesize, has excellent heat resistance, 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 Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). ) (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. ) 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). Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, each consisting of hydrogen or a C1 to C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). ) (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. (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). . Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). ) (However, R ⁶ and R ⁷ may be the same or different,
Hydrogen or a C1-C12 alkyl group, alkenyl group,
It consists of an alkoxy group, an aryl group, an allyloxy group, an alkylamide group, and an arylamide group. (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. Embedded image (Wherein, M is Group 4 transition metal, 5-membered ring is a cyclopentadienyl group, and a substituted cyclopentadienyl M cyclopentadienyl group group eta ⁵ bond π in to have .R ¹ ~ R
⁵ may be the same or different, and any two or three of hydrogen or a C1 to C12 alkyl, alkenyl, alkoxy, aryl, or allyloxy group are bonded to form a ring; The ring also includes those having aromaticity including a conjugated double bond. X, Y, and Z may be the same or different, and each consist of hydrogen or a C1-C12 alkyl group, an alkoxy group, an aryl group, an allyloxy group, or a halogen,
At least one of them comprises a dicarbonyl ligand having a structure represented by the following general formula (2). ) (However, R ⁶ and R ⁷ may be the same or different,
It consists of a C1-C12 alkyl group, alkenyl group, alkoxy group, aryl group, allyloxy group, alkylamide group, and arylamide group. (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.