JPH08176222A - Catalyst for polymerization of olefin and production of olefin polymer - Google Patents

Abstract

PURPOSE: To obtain a catalyst which can give a high-molecular-weight olefin polymer by using a specified metallocene compound and a compound which reacts with the metallocene compound to form a cationic metallocene. CONSTITUTION: This catalyst comprises a substituted-fluorenyl-containing metallocene compound represented by the formula (R<1> is a group which bridges the C5 H4 group and the C4 H4 -mR<2> m C5 H4-n R<3> n group and to heighten the steric rigidity of the compound of the formula and is a aryl-containing hydrocarbon group, silanediyl, germandiyl, C5 H4 : cyclopentadienyl or C4 H4 -mR<2> m C5 H4-n R<3> n : substituted fluorenyl, R<2> and R<3> are each a substituent on the benzo ring of the substituted fluorenyl group, 1-20C amino, a 1-20C oxyhydrocarbon group or a halogen; M<1> is Ti, Zr or Hf; R<4> is H, a hydrocarbon group, a 1-20C amino- or oxy-hydrocarbon group or a halogen; m and n are each an integer of 0-4; and m+n>=1) and a compound which reacts with the metallocene compound to form a cationic metallocene compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention includes a substituted fluorenyl group having an electron-donating substituent on the benzo ring as a ligand, and a cyclopentadienyl group which is the other ligand and the substituted fluorenyl group. A catalyst comprising a metallocene compound characterized by having a cross-linking structure with an aryl group-containing hydrocarbon group, a silanediyl group or a germanediyl group between fluorenyl groups, and a polymerization reaction using the catalyst at a high temperature of 120 ° C. or higher. And a method for obtaining a high molecular weight olefin polymer.

[0002]

2. Description of the Related Art As a complex catalyst showing a high polymerization activity in the polymerization of olefins, a metallocene using a cyclopentadienyl derivative of a transition metal such as titanium, zirconium or hafnium (Group 4 of the periodic table) and aluminoxane as basic constituents. Catalysts have been reported. This known technique is described in J. Boor, "Ziegler-Natta Catalysts and Polymerization," Academic Press. New York
(1979), H .; Sinn and W.D. Kaminsk
y Adv. Organomet. Chem. 189
9 (1980). These catalysts include
The high catalytic activity for olefin polymerization and the ability to produce stereoregular olefin polymers are shown. Further, JP-A-1-503788 discloses the production of high-density polyethylene or a relatively high-density ethylene / α-olefin copolymer by a high-pressure high-temperature method using a metallocene compound which is the above-mentioned catalyst system and aluminoxane. The method is described.

However, the main drawbacks that have hindered the industrial use of these catalysts on a large scale are as follows. First, it is difficult to synthesize aluminoxane used as a cocatalyst in a reproducible form, which makes it difficult to prepare catalysts and polymers with suitable reproducible properties. Second, in order to improve the activity and measure the stability of polymerization, expensive aluminoxane must be used in a remarkably high ratio with respect to the transition metal compound which is the main catalyst.

These drawbacks in catalyst preparation are eliminated by ionic metallocene catalysts. JP-A-3-207
Japanese Patent No. 704 describes an ionic metallocene compound produced by reacting a metallocene compound with an ionized ionic compound. Also, WO92 / 01
Japanese Patent No. 723 describes a method for polymerizing an α-olefin using a catalyst system in which a halogenated metallocene compound is reacted with an organometallic compound and an ionized ionic compound is brought into contact with the reaction product. It is disclosed that various catalyst systems are advantageously used as olefin polymerization catalysts.

Further, Japanese Patent Application Laid-Open No. 5-320246 discloses a high temperature polymerization using this ionic metallocene catalyst. That is, using a conventionally known dicyclopentadienyl zirconium dichloride, an ionic metallocene catalyst is produced from tetra (pentafluorophenyl) boron dimethylanilinium and triisobutylaluminum and used as a polymerization catalyst. However, when the ethylene / 1-octene copolymerization was carried out at a high temperature using the above catalyst, it was reported that the intrinsic viscosity of the produced polymer was small (this suggests that the molecular weight of the polymer is small). Therefore, it is presumed that the rigidity or strength required when the polymer is used alone as a resin is insufficient.

[0006]

Generally, in order to obtain a polymer having a high molecular weight, it is considered that the polymerization temperature is lowered to suppress the chain transfer reaction of the polymerization, but actually, the polymerization is carried out at a temperature lower than the melting point of the polymer. Then, the produced polymer is deposited in the reaction vessel, hinders stirring, and hinders improvement in productivity. This problem is solved in solution polymerization in which the polymerization temperature is set higher than the melting point of the polymer, and it is possible to obtain a homogeneous polymer by decreasing the solution viscosity during polymerization and increasing the stirring efficiency. Further, the heat of polymerization can be easily removed, and the reaction can be advantageously controlled. Further, in the high temperature high pressure polymerization, the greater the difference between the polymerization temperature and the temperature of the feedstock, the better the olefin conversion rate, and the greater the economic benefit. Therefore,
In high temperature polymerization, development of a metallocene catalyst that can be used under higher temperature conditions is required.

The present invention has been made to solve this problem, and its object is to obtain a high molecular weight olefin polymer having a narrow composition distribution and molecular weight distribution in the polymerization at a high temperature of 120 ° C. or higher. An object of the present invention is to provide a manufacturable olefin polymerization catalyst and a method for manufacturing an olefin polymer.

[0008]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the polymerization temperature is 120 ° C. when ethylene is copolymerized or copolymerized with α-olefins. By using a metallocene catalyst having a specific substituent even under the above high temperature, it was found that it is possible to obtain a high molecular weight olefin polymer having a narrow composition distribution and molecular weight distribution, to complete the present invention I arrived.

That is, the present invention comprises: a) the general formula (1)

[0010]

Embedded image

[Wherein R¹Is C_FiveH_FourRadical and C_FourH_4-mR² _mC_Five
C_FourH_4-nR³ _nA compound represented by the general formula (1) by crosslinking a group
Aryl group-containing hydrocarbon group that enhances the steric rigidity of the product,
A landiyl group or a germanediyl group, and C_FiveH_FourBase
Is a cyclopentadienyl group, and C_FourH_4-mR² _mC_FiveC_Four
H_4-nR³ _nThe group is a substituted fluorenyl group, R²And R
³Is a substituent on the benzo ring portion of the substituted fluorenyl group.
Each may be the same or different, and have 1 to 20 carbon atoms.
Amino group, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms,
Is halogen and M¹Is Ti, Zr or Hf
R^FourAre independently hydrogen atom, hydrocarbon group, carbon number
1-20 amino groups, oxygen-containing hydrocarbons having 1-20 carbon atoms
A basic group or halogen, m is an integer of 0 to 4,
n is an integer of 0 to 4, but m + n is at least 1 or more.
Is. ] Having a substituted fluorenyl group represented by
Reacting with a locene compound, and b) a metallocene compound
It consists of compounds that produce cationic metallocene compounds.
Olefin polymerization catalyst, which further comprises c) an organometallic compound
Olefin polymerization catalysts and
The present invention relates to a method for producing a reffin polymer, which will be described below.
The details will be described.

The metallocene compound used in the present invention is
It is represented by the general formula (1).

[0013]

[Chemical 4]

In the formula, R ¹ is a C ₅ H ₄ group and C ₄ H _4-m R ² _m C ₅ C
_An aryl group-containing hydrocarbon group, a silanediyl group or a germanediyl group, which crosslinks a ₄ H _4-n R ³ _n group to increase the steric rigidity of the compound represented by the general formula (1), and preferably an arylalkylene group, An alkylsilanediyl group, an arylsilanediyl group, an alkylgermandiyl group, an arylgermandiyl group, or the like. Specifically, examples of the arylalkylene group include phenylmethylene group, phenylmethylmethylene group, diphenylmethylene group, 1-phenylethylidene group, ditolylmethylene group, dinaphthylmethylene group, etc., and examples of alkylsilanediyl group include dimethylsilane. Diyl group, diethylsilanediyl group, cyclopropylsilanediyl group, etc., phenylmethylsilanediyl group as arylsilanediyl group, diphenylsilanediyl group, ditolylsilanediyl group, etc., dimethylgermandiyl group as an example of alkylgermandiyl group, Examples of the arylgermandiyl group such as a diethylgermandiyl group include a phenylmethylgermandiyl group, a diphenylgermandiyl group, a ditolylgermandiyl group, and the like, and more preferably a ligand-substituted fluorenyl group or a cyclyl group. From the viewpoint of suppressing molecular vibrations of the pentadienyl group, etc., the bridging portion is such that a carbon or silicon single atom bridges the cyclopentadienyl group portion and the 9-position portion of the substituted fluorenyl group, and the phenyl group derivative is bonded to the bridging atom. And a diphenylmethylene group, a diphenylsilanediyl group, a ditolylmethylene group, a ditolylsilanediyl group, a dinaphthylmethylene group or a dinaphthylsilanediyl group.

The fluorenyl skeleton is represented by the following general formula (2).

[0016]

Embedded image

(However, the attached numbers indicate the positions of the substituents of the fluorenyl skeleton.) R ² and R ³ are substituents on the benzo ring portion of the substituted fluorenyl group, and may be the same or different, An amino group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or a halogen, and more preferably an amino group having 1 to 20 carbon atoms and an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms. . Specifically, examples of the amino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group. Group, didecylamino group,
Diisopropylamino group, diisobutylamino group, diisopentylamino group, diphenylamino group, methylphenylamino group, ethylphenylamino group, ditolylamino group, methyltolylamino group, dibenzylamino group, benzylmethylamino group, dinaphthylamino group , Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, etc., having 1 to 2 carbon atoms
Examples of the oxygen-containing hydrocarbon group of 0 are methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group,
Examples thereof include an isobutoxy group, a phenoxy group, a 1-phenylmethoxy group, a naphthoxy group, a 2-methoxymethyl group and a 2-methoxyethyl group.

M ¹ is Ti, Zr or Hf, and R ⁴ is each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Octyl, nonyl, decyl, isopropyl, isobutyl, isopentyl, phenyl, methylphenyl, ethylphenyl, tolyl, methyltolyl, benzyl, naphthyl, cyclopropyl, cyclobutyl, cyclopentyl And a hydrocarbon group such as a cyclohexyl group, and an amino group having 1 to 20 carbon atoms similar to R ² and R ³ , an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, or halogen.

M representing the number of substituents of the fluorenyl group is 0
Is an integer of 4 and n is an integer of 0 to 4, but m + n
Is at least 1 or more, that is, at least one of the hydrogen atoms in the benzo ring portion of the fluorenyl skeleton is replaced by the substituent represented by R ² or R ³ .

Specific examples of the metallocene compound include diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride and diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dimethyl. , Diphenylmethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2
-Diisopropylaminofluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl)
(4-Dimethylaminofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-dimethylaminofluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl) (2-methoxyfluorenyl) zirconium dichloride , Diphenylmethylene (cyclopentadienyl)
(2-methoxyfluorenyl) zirconium dimethyl,
Diphenylmethylene (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl) (2,7 -Dimethoxyfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl) (2,7-bisdimethylaminofluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-
Bisdimethylaminofluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl)
(2-Dimethylaminofluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) ) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl) (4-dimethylaminofluorenyl) zirconium dichloride, diphenylsilanediyl ( Cyclopentadienyl) (4-dimethylaminofluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl) (2-methoxyfluorenyl) di Conium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-methoxyfluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadiene Dienyl) (4-methoxyfluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl) (2,7-dimethoxyfluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7- Dimethoxyfluorenyl) zirconium dimethyl, diphenylsilanediyl (cyclopentadienyl) (2,7-bisdimethylaminofluorenyl) zirconium dichloride, diphenylsilanediyl (cyclo Pentadienyl)
Examples thereof include (2,7-bisdimethylaminofluorenyl) zirconium dimethyl and those in which Zr of the central metal is replaced with Ti or Hf, but the present invention is not limited thereto.

Further, as the compound capable of converting the metallocene compound used herein to a cationic metallocene compound, a protonic acid (3), a Lewis acid (4), an ionizable ionic compound (5), a Lewis acidic compound (6) and Aluminoxane (7), (8) is mentioned.

When the metallocene compound is used as a catalyst, a solvent is provided which forms a cationic metallocene compound including alkylation and hydrolysis of the metallocene compound, protects the produced cationic metallocene compound from catalyst poison, or provides a reaction field. The organometallic compound (9) having at least one alkyl group can be used as the essential role.

The protonic acid used in the present invention is represented by the following general formula (3) [HL ¹ _l ] [M ² R ⁸ ₄ ] (3) (wherein, H is a proton and L ¹ is each independently. Lewis base, l is 0 <l ≦ 2, M ² is a boron atom, an aluminum atom or a gallium atom, and R ⁸
Are each independently a halogen-substituted aryl group having 6 to 20 carbon atoms. ) Is a compound represented by.

The Lewis acid is represented by the following general formula (4) [C] [M ² R ⁸ ₄ ] (4) (wherein C is a carbonium cation or tropylium cation, and M ² is a boron atom or an aluminum atom). Or a gallium atom, and each R ⁸ is independently a halogen-substituted aryl group having 6 to 20 carbon atoms.

The ionized ionic compound is represented by the following general formula (5) [M ³ L ² _r ] [M ² R ⁸ ₄ ] (5) (wherein M ³ is a group 1, 2 or 8 of the periodic table). , 9 groups, 10
Is a cation of a metal selected from Group 11, Group 11 or Group 12, L ² is a Lewis base or a cyclopentadienyl group, r is 0 ≦ r ≦ 2, M ² is a boron atom, an aluminum atom or It is a gallium atom, and each R ⁸ is independently a halogen-substituted aryl group having 6 to 20 carbon atoms. ) Is a compound represented by.

The Lewis acidic compound has the following general formula (6) [M ² R ⁸ ₃ ] (6) (wherein, M ² is a boron atom, an aluminum atom or a gallium atom, and R ⁸ is independently a carbon atom. Number 6 to 20
Is a halogen-substituted aryl group of. ) The compound represented.

Protonic acid (3), Lewis acid (4), ionizable ionic compound (5), Lewis acidic compound (6) and aluminoxane (7), (8) used as a constituent component of the catalyst of the present invention. Is a compound capable of reacting with the above metallocene compound to form a cationic metallocene compound, and is a compound that provides a counter anion to the formed cationic metallocene compound.

Specific examples of the protonic acid represented by the general formula (3) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl). ) Borate, hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) ) Aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) Le) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate,
Examples thereof include N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate and tri-n-butylammonium tetrakis (pentafluorophenyl) aluminate, but are not limited thereto.

Specific examples of the Lewis acid represented by the general formula (4) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, tropi Examples thereof include, but are not limited to, lithium tetrakis (pentafluorophenyl) aluminate.

Specific examples of the ionizable ionic compound represented by the general formula (5) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, and ferrocetes. Ferrocenium salts such as aluminum tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) aluminate, silver tetrakis (pentafluorophenyl) borate, silver salts such as silver tetrakis (pentafluorophenyl) aluminate, or Examples thereof include, but are not limited to, the ether complexes.

Specific examples of the Lewis acidic compound represented by the general formula (6) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane and tris (2,2). 3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum, etc. However, the present invention is not limited to these.

The aluminoxane used in the present invention may have a cyclic or linear form and is represented by the general formula (7) or (8).

[0033]

[Chemical 6]

[0034]

[Chemical 7]

[Wherein p is an integer of 2 or more, R ¹⁰ may be the same or different and is a hydrocarbon group, an alkylamino group or an alkyloxy group, and at least one R 10
¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, isopropyl group, isobutyl group, decyl group, dodecyl group,
Examples include a tetradecyl group and a hexadecyl group. Examples of the organometallic compound used in the present invention include organometallic compounds containing Group 1, 2 or 13 of the periodic table, Sn or Zn, and specifically, the following general formula (9) M ⁴ R ⁹ _s (9) (In the formula, M ⁴ is an element of Group 1, Group 2, Group 13 of the periodic table, Sn or Zn, and R ⁹ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or An alkoxy group, or an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group, wherein at least one R ⁹ is a hydrogen atom or a carbon number of 1 to 20. Is an alkyl group or an aryl group having 6 to 20 carbon atoms, an arylalkyl group, or an alkylaryl group, and s is equal to the oxidation number of M ^4. ).

Examples of the compound represented by the general formula (9) include trimethylaluminum, triethylaluminum, triisopropylaluminum and tri-n-.
Propyl aluminum, triisobutyl aluminum,
Tri-n-butyl aluminum, tripentyl aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-n
-Butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, di-n
-Propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride, etc. can be illustrated.

The catalyst may be prepared by mixing a metallocene compound, a compound capable of converting the metallocene compound into a cationic metallocene compound, and a catalyst component composed of an organometallic compound in a solvent inert to these compounds. There are several types of mixing methods such as a method of contacting a metallocene compound and an organometallic compound in a reaction vessel in which olefins used for polymerization are present, or a combination of the order of mixing each component, but a cationic metallocene compound is formed. The condition is not limited to a specific method.

The amount of protic acid, Lewis acid, ionizable ionic compound or Lewis acidic compound in the catalyst system is
0.1 to 100 times as much as the metallocene compound used
It is preferably ol, and particularly preferably 0.5 to 30 times mol. Furthermore, the amount of the third component organometallic compound used separately is not particularly limited,
Preferably 100,000 times m with respect to the metallocene compound
If it is less than ol and more than this, it becomes necessary to consider the decalcification process. Further, in order to produce a high molecular weight polymer by the catalyst system of the present invention, the amount of the organometallic compound used is preferably as small as possible with respect to the metallocene compound used, for example, an ionized ionic compound and R 2 It is considered that the highest molecular weight can be achieved by polymerizing only the metallocene compound in which ⁴ is an alkyl group or hydrogen, but considering the viewpoints of stabilizing the cationic metallocene compound and eliminating the catalyst poison, the organometallic compound is considered. Is more preferably used in the range of 1 to 1000 times mol.

The amount of aluminoxane used in preparing the catalyst is not particularly limited with respect to the metallocene compound, but is preferably in the range of 10 to 100000 times mol.
If it is less than 0 times mol, the stability of the cationic metallocene compound will be impaired, and if aluminoxane is used in excess of 100,000 times mol, it will be necessary to consider the deashing step. Further, when the polymerization is carried out using methylaluminoxane, which is a typical aluminoxane, the amount used is not limited, but the amount of aluminoxane used is a metallocene compound in order to obtain a high molecular weight polymer. It is better to be less than 10 to 100 in terms of activity and molecular weight.
A range of 00 times mol is preferable, and a range of 10 to 1000 times mo
The l range is most preferred. Further, the organometallic compound represented by the general formula (9) may be mixed with the aluminoxane or metallocene compound in an arbitrary ratio.
1 for the metallocene compound to increase the molecular weight
It is preferably used at 0000 times mol or less.

Examples of α-olefins having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, styrene, p-methylstyrene and the like can be mentioned. In addition, butadiene as a diene,
1,5-hexadiene, 1,4-hexadiene, ethylidene norbornene, vinylidene norbornene and the like may be used in a small amount, but are not limited thereto. Moreover, when performing superposition | polymerization, you may use these 1 type or in mixture of 2 or more types.

Examples of the polymerization method include a solution polymerization method using a solvent and a high temperature / high pressure method, which are known techniques. At this time, as the high pressure process, a vessel type or tubular type reactor or the like is used.

The polymerization conditions in the solution polymerization method are as follows. The polymerization temperature is not particularly limited as long as it is a temperature of 120 ° C. or higher, but the higher the polymerization temperature is, the lower the solution viscosity and the easier removal of the heat of polymerization are. Therefore, it is considered that the productivity of the polymer is improved. From this, 120 ℃ or more 300 ℃
The following temperatures are preferable, but in order to obtain a high molecular weight polymer which is the object of the present invention, the lower the polymerization temperature, the better from the viewpoint of suppressing the chain transfer reaction that lowers the molecular weight of the polymer. It is more preferable to carry out the polymerization at a temperature of 0 ° C or lower. The pressure at the time of polymerization is not particularly limited either, but in view of economy, atmospheric pressure to 200 kg / c
A range of m ² is preferred.

The polymerization conditions in the high temperature / high pressure method are as follows, and the polymerization temperature is not particularly limited as long as it is a temperature of 120 ° C. or higher, but the productivity of the polymer can be improved due to the reasons described above in the solution polymerization. From the viewpoint, a temperature of 120 ° C. or higher and 300 ° C. or lower is preferable, but from the viewpoint of suppressing the chain transfer reaction that lowers the molecular weight of the polymer, it is more preferable to carry out at a polymerization temperature of 120 ° C. or higher and 250 ° C. or lower. The polymerization pressure is not particularly limited, but it is 5 from the viewpoint of polymer productivity.
It is preferably carried out under a pressure of 00 to 3500 kg / cm ² .

[0044]

EFFECTS OF THE INVENTION According to the present invention, a high molecular weight olefin polymer having a narrow composition distribution and a molecular weight distribution and capable of efficiently producing a high molecular weight olefin polymer is obtained in the polymerization at a high temperature such that the obtained polymer is melted. You can

[0045]

EXAMPLES In order to explain the present invention in more detail by way of examples, the results of synthesis and polymerization of metallocene compounds will be illustrated below, but the present invention is not limited to these examples.

Polymerization operations, reactions and solvent purification were all carried out under an inert gas atmosphere of purified argon or dry nitrogen. All the solvents used in the reaction were previously purified, dried and / or deoxygenated by known methods. As the compound used in the reaction, a known technique was used or a compound synthesized and identified by applying it was used.

The olefin polymer obtained in the present invention is a gel permeation chromatography (GPC) (W
Column TSK using ATERS 150C type)
-GEL GMHHR-H (S), eluent o-dichlorobenzene, measurement temperature 140 ° C, measurement concentration 7 mg (sample) / 10 ml (o-dichlorobenzene).

The MFR (melt flow rate) is
The measurement was carried out by a method according to ASTM D1238 Condition E.

Further, the identification of the metallocene compound is carried out by ¹ H
-NMR (400M) (GX-40 manufactured by JEOL Ltd.)
0).

Reference Example 1 Synthesis of diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride 4.26 g of 2-dimethylaminofluorene and 250 m of tetrahydrofuran (THF) in a 1 L Schlenk container.
1 was introduced, the mixture was cooled to −78 ° C., and 11 ml of 1.72N hexane solution n-butyllithium (n-BuLi) was slowly added dropwise. The temperature of the reaction solution was naturally raised, and when it reached room temperature, it was cooled to -78 ° C again, and a solution of 5.1 g of diphenylfulvene in THF (250 ml) was slowly added dropwise. The temperature was raised naturally while stirring vigorously overnight to obtain a red homogeneous solution. After washing the reaction solution with saturated saline,
The solvent was distilled off and the residue was purified by column chromatography,
6 g of a slightly yellowish white solid was obtained. This solid 2.
2 g was put into another Schlenk container, 250 ml of THF was added, and the mixture was cooled to -78 ° C. 6.5 ml of n-BuLi of 1.72N hexane solution was slowly added dropwise thereto, and the temperature was naturally raised to room temperature. A solution prepared by dissolving 1.15 g of zirconium tetrachloride in 100 ml of THF was slowly introduced into this reaction solution to obtain 1.15 g of the objective diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride. The results of ¹ H-NMR measurement used for identifying this compound are shown in Table 1.

Reference Example 2 Synthesis of diphenylmethylene (cyclopentadienyl) (2-diethylaminofluorenyl) zirconium dichloride Synthesis was performed in the same manner as in Reference Example 1 except that 2-dimethylaminofluorene was changed to 2-diethylaminofluorene. It was

Reference Example 3 Synthesis of diphenylmethylene (cyclopentadienyl) {2,7-bis (diethylamino) fluorenyl} zirconium dichloride Reference was made except that 2-dimethylaminofluorene was changed to 2,7-bis (diethylamino) fluorene. Synthesis was performed in the same manner as in Example 1.

Reference Example 4 Synthesis of diphenylmethylene (cyclopentadienyl) {2,7-bis (diethylamino) fluorenyl} hafnium dichloride Synthesis was performed in the same manner as in Reference Example 3 except that zirconium tetrachloride was changed to hafnium tetrachloride. It was

[0054]

[Table 1]

Reference Example 5 Synthesis of diphenylmethylene (cyclopentadienyl) (2-methoxyfluorenyl) zirconium dichloride Synthesis was performed in the same manner as in Reference Example 1 except that 2-dimethylaminofluorene was changed to 2-methoxyfluorene. It was

[0056]

[Table 2]

Example 1 As a solvent, an aliphatic hydrocarbon (IP Solvent 1620) was used.
(Manufactured by Idemitsu Petrochemical Co., Ltd.) 600 ml was added to a 1 liter reactor, and the temperature of the reactor was set to 170 ° C. Then, ethylene was supplied to this reactor so that the pressure became 20 kg / cm ² .

On the other hand, in another container, diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride 1.0 μmol
Is dissolved in toluene, and a toluene solution of triisobutylaluminum (triisobutylaluminum 20 w
t%) was added in an amount of 100 μmol in terms of aluminum and stirred for 1 hour. Next, this mixture was added to a solution in which 1.2 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 1 ml of toluene and stirred for 10 minutes, and the mixture obtained here was added to the reactor under nitrogen pressure. Supplied to.

After supplying the mixture to the reactor, the temperature was raised to 170 ° C., and in this state, the reactor was stirred at 1500 rpm for 20 minutes to carry out a polymerization reaction. The polymer obtained was dried under vacuum at 100 ° C. for 6 hours. As a result, 30.8g
Polyethylene was obtained. Table 3 shows the measurement results of MFR and the like of the obtained polymer.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the amount of triisobutylaluminum was 250 μmol. The results are shown in Table 3.

Example 3 1-Hexene 20 was added immediately after introducing the solvent into the reactor.
Example 2 except that ml was introduced into the reactor and copolymerization was performed.
Polymerization was carried out in the same manner as in. The results are shown in Table 3.

Comparative Example 1 As a solvent, an aliphatic hydrocarbon (IP Solvent 1620) was used.
(Manufactured by Idemitsu Petrochemical Co., Ltd.) 600 ml was added to a 1 l reactor, and immediately 20 ml of 1-hexene was introduced into the reactor,
The reactor temperature was set at 170 ° C. Then, ethylene was supplied to this reactor so that the pressure became 20 kg / cm ² .

On the other hand, in another container, 1.0 μmol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was dissolved in toluene, and a toluene solution of triisobutylaluminum (triisobutylaluminum 20 wt%) was converted to aluminum. 250 μmol was added and stirred for 1 hour. Next, this mixture was mixed with N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 1.2 μm.
was added to a solution dissolved in 1 ml of toluene and stirred for 10 minutes, and the mixture obtained here was supplied to the reactor under nitrogen pressure.

After supplying the mixture to the reactor, the temperature was raised to 170 ° C., and in this state, the reactor was stirred at 1500 rpm for 20 minutes to carry out a copolymerization reaction. The obtained copolymer was dried under vacuum at 100 ° C. for 6 hours. The molecular weight of the obtained copolymer was low as compared with the case where the catalyst of the present invention was used. The results are shown in Table 3.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that the amount of triisobutylaluminum was 4 mmol. The results are shown in Table 3.

Example 5 Polymerization was carried out in the same manner as in Example 2 except that trimethylaluminum was used instead of triisobutylaluminum. The results are shown in Table 3.

Example 6 Polymerization was carried out in the same manner as in Example 1 except that the amount of triisobutylaluminum was 1 mmol. The results are shown in Table 3.

[0068]

[Table 3]

Example 7 Aliphatic hydrocarbons (IP Solvent 1620 as a solvent)
(Manufactured by Idemitsu Petrochemical Co., Ltd.) 600 ml was added to a 1 liter reactor, and the temperature of the reactor was set to 170 ° C. Then, ethylene was supplied to this reactor so that the pressure became 20 kg / cm ² .

On the other hand, in another container, diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride 1.0 μmol
Is dissolved in toluene, and a toluene solution of methylaluminoxane (20% by weight solution of methylaluminoxane manufactured by Tosoh Akzo Co., Ltd.) is added thereto in 1000 equivalents of aluminum.
μmol was added to make a 10 ml toluene solution, and the mixture was stirred for 1 hour. The mixture obtained here was fed to the reactor under nitrogen pressure.

After the mixture was supplied to the reactor, the internal temperature of the reactor was maintained at 170 ° C., the mixture was stirred at 1500 rpm for 20 minutes to carry out a polymerization reaction, and the obtained polymer was heated to 100 ° C. under vacuum.
Dry at 6 ° C for 6 hours. As a result, 30.6 g of polyethylene was obtained. Table 4 shows the measurement results of MFR and the like of the obtained polymer.

Comparative Example 2 Aliphatic hydrocarbon (IP Solvent 1620 as a solvent)
(Manufactured by Idemitsu Petrochemical Co., Ltd.) 600 ml was added to a 1 liter reactor, and the temperature of the reactor was set to 170 ° C. Then, ethylene was supplied to this reactor so that the pressure became 20 kg / cm ² .

On the other hand, in another container, 1.0 μmol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was dissolved in toluene, and a toluene solution of methylaluminoxane (methylaluminoxane manufactured by Tosoh Akzo Co., Ltd.) was added thereto. 20 wt%
1) by adding 1000 μmol of aluminum solution)
The solution was made into 0 ml of toluene and stirred for 1 hour. The mixture obtained here was fed to the reactor under nitrogen pressure.

After the mixture was supplied to the reactor, the internal temperature of the reactor was maintained at 170 ° C., the mixture was stirred at 1500 rpm for 20 minutes to carry out a polymerization reaction, and the obtained polymer was heated under vacuum to 100 ° C.
Dry at 6 ° C for 6 hours. As a result, 24.3 g of polyethylene was obtained. Table 4 shows the measurement results of MFR and the like of the obtained polymer.

Example 8 1-Hexene 20 was added immediately after introducing the solvent into the reactor.
Polymerization was performed in the same manner as in Example 1 except that 100 ml of ethylidene norbornene and 10 ml of ethylidene norbornene were introduced into the reactor and copolymerization was performed. The results are shown in Table 4.

Example 9 Polymerization was carried out in the same manner as in Example 7 except that the amount of methylaluminoxane was changed to 4 mmol. The results are shown in Table 4.

Example 10 Polymerization was carried out in the same manner as in Example 7 except that the amount of methylaluminoxane was changed to 10 mmol. The results are shown in Table 4.

Example 11 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) {2.
Polymerization was performed in the same manner as in Example 1 except that 7-bis (diethylamino) fluorenyl} zirconium dichloride was used. The results are shown in Table 4.

Example 12 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) {2.
Polymerization was performed in the same manner as in Example 4 except that 7-bis (diethylamino) fluorenyl} zirconium dichloride was used. The results are shown in Table 4.

[0080]

[Table 4]

Example 13 1-Hexene 20 was added immediately after introducing the solvent into the reactor.
Polymerization was carried out in the same manner as in Example 1 except that ml was introduced into the reactor and the copolymerization was carried out at 200 ° C. The results are shown in Table 5.

Example 14 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) (2-
Polymerization was carried out in the same manner as in Example 13 except that diethylaminofluorenyl) zirconium dichloride was used.
The results are shown in Table 5.

Example 15 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) {2.
Polymerization was performed in the same manner as in Example 1 except that 7-bis (diethylamino) fluorenyl} zirconium dichloride was used and the copolymerization was performed at 200 ° C. The results are shown in Table 5.

Example 16 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) {2.
Copolymerization was performed in the same manner as in Example 13 except that 7-bis (diethylamino) fluorenyl} hafnium dichloride was used. The results are shown in Table 5.

[0085]

[Table 5]

Example 17 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride 650 μmol / l, triisobutylaluminum 1
62.5 mmol / l, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 78
A toluene solution of a catalyst consisting of 0 μmol / l was introduced into a high-pressure reaction vessel, and the ethylene pressure was 900 kg / c.
Ethylene and 1-hexene were continuously supplied so that the concentration of m ² and 1-hexene was 32 mol%, and polymerization was continuously performed while maintaining the reaction temperature at 200 ° C.

As a result, 157 kg per mmol Zr
Was obtained. When the physical properties of the obtained polymer were measured, MFR 1.3 g / 10 min. , Density 0924g
Was / cc. The results are shown in Table 6. Comparative Example 3 Except that diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was changed to diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride. Polymerization was carried out in the same manner as in Example 17. The results are shown in Table 6, and the MFR was 9.3 g / 10 min. Thus, only a polymer having a low molecular weight was obtained as compared with Example 17.

Example 18 Polymerization was carried out in the same manner as in Example 17 except that the 1-hexene concentration was changed to 36 mol% and the copolymerization was carried out at 210 ° C. The results are shown in Table 6.

Comparative Example 4 Polymerization was performed in the same manner as in Comparative Example 3 except that the 1-hexene concentration was changed to 36 mol% and the copolymerization was performed at 210 ° C.
The results are shown in Table 6.

[0090]

[Table 6]

Example 19 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) (2-
Copolymerization was performed in the same manner as in Example 3 except that methoxyfluorenyl) zirconium dichloride was used. The results are shown in Table 7.

Example 20 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) (2-
Copolymerization was performed in the same manner as in Example 3 except that methoxyfluorenyl) zirconium dichloride was used and the copolymerization was performed at 200 ° C. The results are shown in Table 7.

Example 21 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) (2-
Copolymerization was performed in the same manner as in Example 3 except that methoxyfluorenyl) zirconium dichloride was used and the amount of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was 2.0 μmol. The results are shown in Table 7.

Example 22 Diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride was added to diphenylmethylene (cyclopentadienyl) (2-
Copolymerization in the same manner as in Example 3 except that methoxyfluorenyl) zirconium dichloride was used and the amount of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was 2.0 μmol and the copolymerization was carried out at 200 ° C. I went. The results are shown in Table 7.

[0095]

[Table 7]

Claims (8)

[Claims] 1. a) General formula (1): [Wherein R ¹ is a C ₅ H ₄ group and C ₄ H _4-m R ² _m C ₅ C ₄ H _4-n R ³ _n
An aryl group-containing hydrocarbon group, a silanediyl group or a germanediyl group, which crosslinks the group to enhance the steric rigidity of the compound represented by the general formula (1), and the C ₅ H ₄ group is a cyclopentadienyl group. , C ₄ H _4-m R ² _m C ₅ C ₄ H _4-n R ³ _n group is a substituted fluorenyl group, R ² and R ³ are substituents on the benzo ring part of the substituted fluorenyl group, The same or different, an amino group having 1 to 20 carbon atoms,
Is an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or halogen, M ¹ is Ti, Zr or Hf, R ⁴ is each independently a hydrogen atom, a hydrocarbon group, an amino group having 1 to 20 carbon atoms, It is an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or halogen, m is an integer of 0 to 4, n is an integer of 0 to 4, and m + n is at least 1 or more. ] The metallocene compound which has the substituted fluorenyl group shown by these, and b) the compound which reacts with a metallocene compound and produces | generates a cationic metallocene compound. 2. a) General formula (1): [Wherein R ¹ is a C ₅ H ₄ group and C ₄ H _4-m R ² _m C ₅ C ₄ H _4-n R ³ _n
An aryl group-containing hydrocarbon group, a silanediyl group or a germanediyl group, which crosslinks the group to enhance the steric rigidity of the compound represented by the general formula (1), and the C ₅ H ₄ group is a cyclopentadienyl group. , C ₄ H _4-m R ² _m C ₅ C ₄ H _4-n R ³ _n group is a substituted fluorenyl group, R ² and R ³ are substituents on the benzo ring part of the substituted fluorenyl group, The same or different, an amino group having 1 to 20 carbon atoms,
Is an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or halogen, M ¹ is Ti, Zr or Hf, R ⁴ is each independently a hydrogen atom, a hydrocarbon group, an amino group having 1 to 20 carbon atoms, It is an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or halogen, m is an integer of 0 to 4, n is an integer of 0 to 4, and m + n is at least 1 or more. ] The metallocene compound which has a substituted fluorenyl group shown by these, b) the compound which reacts with a metallocene compound and produces | generates a cationic metallocene compound, and c) an olefin polymerization catalyst which consists of an organometallic compound. 3. A compound b) which reacts with a metallocene compound to form a cationic metallocene compound, provides a counter anion to the metallocene, a Lewis acid,
The olefin polymerization catalyst according to claim 1 or 2, which is an ionized ionic compound or a Lewis acidic compound. 4. The catalyst for olefin polymerization according to claim 1 or 2, wherein the compound b) which reacts with the metallocene compound to form a cationic metallocene compound is aluminoxane. 5. The olefin polymerization catalyst according to claim 2, wherein the organometallic compound comprises a component containing an organoaluminum compound. 6. The number of aluminum atoms in the organoaluminum compound is 1 with respect to the number of transition metal atoms in the metallocene compound.
It is 000 times or less, The olefin polymerization catalyst of Claim 5 characterized by the above-mentioned. 7. The number of aluminum atoms in the aluminoxane is 100 relative to the number of transition metal atoms in the metallocene compound.
It is 0 times or less, The olefin polymerization catalyst of Claim 4 characterized by the above-mentioned. 8. The olefin polymerization catalyst according to claim 1, which is used for ethylene and / or α-containing 3 or more carbon atoms.
A method for producing an olefin polymer, which comprises polymerizing an olefin at a temperature of 120 ° C. or higher.