JPH11236406A - Catalyst component for olefin polymerization, catalyst for olefin polymerization, and production of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst component having high activities at a reaction temperature at which an industrial process is efficiently carried out, and enabling the synthesis of a polyolefin with a high molecular weight by making the catalyst component include a specific transition metal compound. SOLUTION: This catalyst component is a transition metal compound of formula I [M is a group IV transition metal in the periodic table; L is a group of formula II (R<1> and R<2> are each an aryl or a substituted aryl; A and B are each a group XV element in the periodic table, D is a group XIV atom, with the proviso that A is bonded to M, and B coordinates with M by a lone electron-pair or is bonded thereto by other means; R<3> is H, an aliphatic hydrocarbon or the like); Cp is cyclopentadienyl or the like; (m) is 1 or 2; when (m) is 1, (n) is 1, and when (m) is 2, (n) is 0; X<1> and X<2> are each H, a halogen, an organic metalloid or the like]. The M in the compound of formula I is preferably zirconium. The catalyst component preferably includes an organic aluminum hydroxy compound or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel olefin polymerization catalyst component, an olefin polymerization catalyst containing the component, and a method for producing a polyolefin using the catalyst. More specifically, a catalyst component for olefin polymerization having high activity and capable of obtaining a high molecular weight polyolefin,
The present invention relates to an olefin polymerization catalyst containing the component and a method for producing a high-molecular-weight polyolefin using the catalyst.

[0002]

2. Description of the Related Art As a homogeneous catalyst for olefin polymerization, a catalyst comprising a combination of a metallocene compound and an organic aluminum oxy compound is widely known. For example, JP-A-58-19309, JP-A-60-35007, Makromol.Chem., R
apid Commun. 9, 457-461 (1988) and others report polymerization catalysts for olefins comprising various metallocene compounds and linear or cyclic organoaluminumoxy compounds. However, with the biscyclopentadienyl complex system used in these conventional techniques, a high-molecular-weight polyolefin cannot be obtained when polymerization is carried out at a reaction temperature of 50 ° C to 200 ° C, which is efficient in an industrial process.

In Japanese Patent Application Laid-Open No. 7-2917, an amidinato complex having a trimethylsilyl group on a nitrogen atom is disclosed.
Specifically, bis (N, N′-bis (trimethylsilyl)
(Benzamidinato) zirconium dichloride, bis (N, N′-bis (trimethylsilyl) benzamidinato) zirconium ditriflate, (cyclopentadienyl) (N, N′-bis (trimethylsilyl) benzamidinato) titanium Dichloride, (cyclopentadienyl) (N, N'-bis (trimethylsilyl) benzamidinato) zirconium chloride, (pentamethylcyclopentadienyl) (N, N'-bis (trimethylsilyl) benzamidinato) titanium It is described that high molecular weight polyolefins can be obtained by polymerization using dichloride, but these are not sufficiently satisfactory for industrial production due to their low polymerization activity.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a catalyst system capable of producing a polyolefin having a high activity and a high molecular weight at a reaction temperature of 50 ° C. or higher at which an industrial process can be carried out efficiently. To provide.

[0005]

Means for Solving the Problems The present inventors have found that the above problems can be solved by using a catalyst component comprising a transition metal compound having a specific structure, and have reached the present invention. Hereinafter, the present invention will be described in detail.

First, the catalyst component for olefin polymerization of the present invention comprises a transition metal compound (A) represented by the following general formula (1).

(L) _m (Cp) _n MX ¹ X ² (1) In the formula, M means a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, or hafnium; Preferably, it is zirconium.

L is a general formula (2) (Wherein, R ¹ and R ² are aryl or substituted aryl groups, which may be the same or different. A and B may be the same or different and are each an atom of Group 15 of the periodic table. , D is an atom of Group 14 of the periodic table of the periodic table, A is bonded to M, B is coordinated by a lone pair of electrons, or between M, A, D and B When resonating, they are bound by the resonance, and R ³ is
It is a hydrogen atom, an aliphatic hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ³ may be cross-linked to R ¹ or R ² . ).

Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group, m is 1 or 2, and n is 1 Hour is 1, when m is 2, it is 0, and when m is 1, L group and C
It may be cross-linked with a p group, and when m is 2, L
X ¹ and X ² may be the same or different, and each may be a hydrogen atom, a halogen atom, an organic metalloid group, an alkoxy group, an amino group,
It is a hydrocarbon group or a heteroatom-containing hydrocarbon group.

In the present invention, R ³ is preferably a hydrogen atom and an aliphatic hydrocarbon having 1 to 20 carbon atoms.
~ 6 linear hydrocarbon groups are preferred.

Hereinafter, specific examples of the Group 4 transition metal compound represented by the general formula (1) when M is zirconium will be exemplified. (Pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N'-di (p-tolyl) formamidinato) zirconium dichloride, (Pentamethylcyclopentadienyl) (N, N′-dinaphthylformamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N′-diphenylacetamidominato) zirconium dichloride, (pentamethylcyclopenta Dienyl) (N, N′-di (p-tolyl) acetamidinato) zirconium dichloride,
(Pentamethylcyclopentadienyl) (N, N'-dinaphthyl acetamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N '
-Diphenylethylamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N,
N′-diphenyl-tert-butylamidinato) zirconium dichloride, (cyclopentadienyl) (N,
(N′-diphenylformamidinato) zirconium dichloride, (cyclopentadienyl) (N, N′-diphenylacetamidinato) zirconium dichloride,
(N-propylcyclopentadienyl) (N, N'-diphenylformamidinato) zirconium dichloride, (n-propylcyclopentadienyl) (N, N '
-Diphenylacetamidinato) zirconium dichloride, (n-butylcyclopentadienyl) (N, N '
-Diphenylformamidinato) zirconium dichloride, (n-butylcyclopentadienyl) (N, N '
-Diphenylacetamidinato) zirconium dichloride,

(Indenyl) (N, N'-diphenylformamidinato) zirconium dichloride, (indenyl) (N, N'-diphenylacetamidinato) zirconium dichloride, (trimethylindenyl)
(N, N'-diphenylformamidinato) zirconium dichloride, (trimethylindenyl) (N, N '
-Diphenylacetamidinato) zirconium dichloride, (tetrahydroindenyl) (N, N'-diphenylformamidinato) zirconium dichloride,
(Tetrahydroindenyl) (N, N'-diphenylacetamidinato) zirconium dichloride, bis (N, N'-diphenylformamidinato) zirconium dichloride, bis (N, N'-di (p-tolyl) formamidi Nato) zirconium dichloride, bis (N, N'-dinaphthylformamidinato) zirconium dichloride, bis (N, N'-diphenylacetamidominato) zirconium dichloride, bis (N, N ')
-Di (p-tolyl) acetamidinato) zirconium dichloride, bis (N, N'-dinaphthylacetamidinato) zirconium dichloride,

Methylene (cyclopentadienyl) (N,
N'-diphenylamidinato) zirconium dichloride, ethylene (cyclopentadienyl) (N, N'-diphenylamidinato) zirconium dichloride, isopropylidene (cyclopentadienyl) (N, N'-diphenylamidinato ) Zirconium dichloride, methylene (n-butylcyclopentadienyl) (N, N'-
Diphenylamidinato) zirconium dichloride, ethylene (n-butylcyclopentadienyl) (N, N ′
-Diphenylamidinato) zirconium dichloride,
Isopropylidene (n-butylcyclopentadienyl)
(N, N'-diphenylamidinato) zirconium dichloride, methylene (tetramethylcyclopentadienyl) (N, N'-diphenylamidinato) zirconium dichloride, ethylene (tetramethylcyclopentadienyl) (N, N '-Diphenylamidinato) zirconium dichloride, isopropylidene (tetramethylcyclopentadienyl) (N, N'-diphenylamidinato) zirconium dichloride, methylenebis (N,
Examples thereof include (N′-diphenylamidinato) zirconium dichloride, ethylenebis (N, N′-diphenylamidinato) zirconium dichloride, and isopropylidenebis (N, N′-diphenylamidinato) zirconium dichloride.

Of these, (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) zirconium dichloride and (pentamethylcyclopentadienyl) (N, N'-diphenylacetamidina) are preferred. G) Zirconium dichloride.

As an example of the transition metal compound of the general formula (1) wherein the Group 4 transition metal M which can be used in the present invention is hafnium or titanium, zirconium is replaced by hafnium or titanium in the above specific examples of the zirconium compound. What was done.

Next, the first to fourth olefin polymerization catalysts of the present invention containing the above-mentioned transition metal compound (A) as a catalyst component will be described. FIG. 1 shows the steps of preparing an olefin polymerization catalyst according to the present invention.

First, the first catalyst for olefin polymerization according to the present invention comprises a transition metal compound (A) represented by the general formula (1), an organoaluminum oxy compound (B-1) and the general formula (1). And at least one compound (B) selected from the group consisting of compounds (B-2) which form an ion pair by reacting with the transition metal compound represented by the formula (1).

The second olefin polymerization catalyst according to the present invention comprises a transition metal compound (A) represented by the general formula (1).
And at least one compound selected from the group consisting of an organic aluminum oxy compound (B-1) and a compound (B-2) which forms an ion pair by reacting with the transition metal compound represented by the general formula (1). (B) and at least one compound (C) selected from organic lithium, organic magnesium and organic aluminum.

The third olefin polymerization catalyst according to the present invention comprises a transition metal compound (A) represented by the general formula (1).
And at least one compound selected from the group consisting of an organic aluminum oxy compound (B-1) and a compound (B-2) which forms an ion pair by reacting with the transition metal compound represented by the general formula (1). (B) and a carrier (D).

The fourth olefin polymerization catalyst according to the present invention is a transition metal compound (A) represented by the general formula (1).
And at least one compound selected from the group consisting of an organic aluminum oxy compound (B-1) and a compound (B-2) which forms an ion pair by reacting with the transition metal compound represented by the general formula (1). (B), at least one compound (C) selected from organolithium, organomagnesium, and organoaluminum, and a carrier (D).

The organoaluminum oxy compound (B-B) used in the catalyst for polymerizing the first to fourth olefins of the present invention.
As 1) (hereinafter sometimes referred to as “component (B-1)”), an aluminoxane-based compound is usually preferably used, but a modified aluminoxane can also be used as described later.

A typical example of the above aluminoxane is a compound represented by the general formula (3) or (4).

In the formula, R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group or a halogenated aryl group. Here, examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group and the like, and preferably a methyl group and an isobutyl group. However, a plurality of R ⁴ in the same formula may be the same or different. That is, a substituent such as a hydrocarbon group may be arbitrarily contained, for example, a repeating unit having a different hydrocarbon group may be bonded in a block manner, or may be bonded regularly or irregularly. It may be something. m is 1 to 100, preferably 4 or more, particularly preferably 8 or more.

A method for producing this kind of compound is known, for example, a method of adding an organoaluminum compound to a hydrocarbon solvent suspension of a salt having water of crystallization (copper sulfate hydrate, aluminum sulfate hydrate). It can be produced by a method in which solid, liquid or gaseous water is allowed to act on an organic aluminum compound in a hydrocarbon solvent. In this case, the compound of the general formula (3) or (4) is
Species or more of them may be used as a mixture.

Examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trinormalbutylaluminum, triisobutylaluminum, and tri-aluminum.
trialkylaluminums such as sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tricyclohexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride and diisobutylaluminum chloride; Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum methoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide are selected. Of these, trialkylaluminums, particularly trimethylaluminum and triisobutylaluminum, are preferred.

The hydrocarbon solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; cyclopentane; Examples thereof include alicyclic hydrocarbons such as cyclohexane. Of these solvents, aromatic hydrocarbons are preferred.

At least one compound selected from the group consisting of compounds which react with the transition metal compound represented by the general formula (1) to form an ion pair used in the first to fourth olefin polymerization catalysts of the present invention. Compound (B-2) (hereinafter sometimes referred to as “component (B-2)”) is described in JP-A-1-501950, JP-A-1-502036, and JP-A-3,050 / 96.
-179005, JP-A-3-179006, JP-A-3-20770
No. 3, JP-A-3-207704, etc., Lewis acids, ionic compounds and carborane compounds.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-
Tolyl) boron, tris (o-tolyl) borane, tris (3,5-dimethylphenyl) boron, tris (pentafluorophenyl) _{boron, MgCl 2, Al 2 O 3} , S
iO ₂ -AlO ₃ can be exemplified.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, trinormalbutylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocetone. Examples thereof include tetrakis (pentafluorophenyl) borate.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, and tri-n-butylammonium (trideca hydride-7-carboundeca) borate. Further, the component (B-2) which forms an ion pair by reacting with the transition metal compound (A) can be used as a mixture of two or more kinds.

At least one compound (C) selected from organolithium, organomagnesium and organoaluminum used in the second and fourth olefin polymerization catalysts according to the present invention (hereinafter referred to as “component (C)”) The following may be specifically mentioned.

As the organic lithium, methyl lithium,
Ethyl lithium, normal propyl lithium, normal butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, normal pentyl lithium, isopentyl lithium, neopentyl lithium, and the like. Among these, normal butyl lithium and tert-butyl lithium are preferred.

Examples of the organic magnesium include normal butyl ethyl magnesium, di-sec-butyl magnesium, normal butyl-sec-butyl magnesium, and di-t-butyl magnesium.
ert-butyl magnesium, dineopentyl magnesium, dinormal hexyl magnesium, and the like.
Among these, normal butyl ethyl magnesium,
Di-sec-butylmagnesium and dinormalhexylmagnesium are preferred.

Further, as the organic aluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trinormalbutylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum
Butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tricyclohexyl aluminum and the like. Of these, trimethylaluminum and triisobutylaluminum are preferred. The above component (C) can be used as a mixture of two or more kinds.

The carrier (D) used in the third and fourth olefin polymerization catalysts according to the present invention (hereinafter sometimes referred to as “component (D)”) is a porous fine particle carrier, A solid that is solid in the polymerization medium is preferred, and is selected from inorganic oxides, inorganic chlorides, inorganic carbonates, inorganic sulfates, and organic polymers.

As a specific example of the inorganic oxide, for example, Si
_{O 2, Al 2 O 3,} MgO, ZrO 2, TiO 2, CaO inorganic oxide or _{SiO 2 -Al 2 O 3, SiO} 2 -Mg
O, SiO ₂ —ZrO ₂ , SiO ₂ —TiO ₂ , SiO ₂ —
_{CaO, Al 2 O 3 -MgO,} Al 2 O 3 -ZrO 2, Al 2
O ₃ —TiO ₂ , Al ₂ O ₃ —CaO, ZrO ₂ —TiO ₂ ,
ZrO ₂ -CaO, ZrO ₂ -MgO, TiO ₂ -MgO
Such as complex oxides, inorganic chlorides such as magnesium chloride, magnesium carbonate, calcium carbonate, inorganic carbonates such as strontium carbonate, magnesium sulfate, calcium sulfate,
Inorganic sulfates such as barium sulfate;

Specific examples of the organic polymer carrier include fine particles of polyethylene, polypropylene, polystyrene and the like. Among these, inorganic oxides, especially SiO 2
₂ , it is desirable to be selected from Al ₂ O ₃ and its composite oxide.

The average particle size of the porous fine particle carrier is 1 to
It is 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. The specific surface area is 10
It is preferably in the range of 1000 m ² / g, more preferably 100 m ² / g.
８００800 m ² / g is preferred, especially 200 to 60 m ² / g.
A range of 0 m ² / g is preferred. Also, the pore volume is 0.3 ~
The range is preferably 3 cm ³ / g, more preferably 0.5 to 2.5 cm ³ / g
Is particularly preferable, and a range of 1.0 to 2.0 cm ³ / g is particularly preferable.

The amount of water adsorbed and the amount of surface hydroxyl groups of SiO ₂ , Al ₂ O _3, and their composite oxides, which are preferably used in the present invention, vary depending on the treatment conditions. As a preferable range thereof, the water content is 5% by weight or less, and the surface hydroxyl group content is
(Nm) ² or more. The water content and the amount of surface hydroxyl groups can be controlled by baking treatment (selection of baking temperature and baking time) and treatment with an organic aluminum compound, an organic boron compound, or the like.

In the first to fourth olefin polymerization catalysts according to the present invention, the ratio of the component (A) to the component (B) is determined by the molar ratio when the component (B) is (B-1). Preferably from 1: 1 to 1: 10000, more preferably from 1:10
1: 1000 is desirable, and the component (B) is the component (B-
In the case of 2), the molar ratio is preferably 10: 1 to 1: 1.
00, more preferably in the range of 2: 1 to 1:10. Further, the molar ratio of component (A) to component (C) in the second and fourth olefin polymerization catalysts is preferably 1:10 to 1: 100000, and more preferably 1:10.
The range of 0 to 1: 10000 is desirable.

In the third and fourth olefin polymerization catalysts of the present invention, the proportion of the component (B) to the component (D) is, in the case of the component (B-1), a weight ratio, preferably 1 : 0.5 to 1: 100, more preferably 1: 1 to 1: 1
0 is preferable, and in the case of the component (B-2), the weight ratio is preferably 1: 1 to 1: 10000, and more preferably 1: 5 to 1: 100. Further, the use ratio of the component (A) to the component (D) is preferably from 1: 5 to 1: 10000, more preferably from 1:10 to 1: 1, by weight.
A range of 500 is desirable.

In the first to fourth polyolefin production catalysts, each component is contacted at the time of the polymerization reaction with an aromatic hydrocarbon such as benzene, toluene, xylene, or an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or decane. hydrogen,
The reaction can be performed in an alicyclic hydrocarbon such as cyclopentane or cyclohexane, in the presence or absence of an olefin.

The temperature at the time of contact is from -70 ° C. to 200
° C, preferably -20 ° C to 120 ° C, and the mixing time is 1 minute to 60 minutes. In preparing the first to fourth polyolefin-producing catalysts during the polymerization reaction, the contact time of each component of the catalyst can be arbitrarily selected. For example, the component (A) is brought into contact with the component (B) in advance,
A method in which the component (C) and the olefin to be used for the polymerization are charged into a reaction vessel, and the polymerization reaction is started by adding the olefin to the reaction vessel. Alternatively, the polymerization reaction may be started by charging the component (C) and the olefin to be used for polymerization in a reaction vessel, and separately adding the component (A) and the component (B). In particular, in the third and fourth catalysts for producing polyolefins according to the present invention, it is desirable that at least one of the component (A) and the component (B) is supported on the component (D).

The method of loading is not particularly limited. For example, (1) a method of mixing at least one of the components (A) and (B) with the component (D), and (2) a component (D)
Is treated with component (C) or a halogen-containing silicon compound, and then at least one of components (A) and (B) is mixed with component (D). (3) Component (D) and component (A) And / or a method of reacting the component (B) with the component (D) or the halogen-containing silicon compound. (4) After the component (A) or the component (B) is supported on a carrier, the component (B) or the component (A) ), (5) a method in which a contact product of the component (A) and the component (B) is brought into contact with a carrier, and (6) a carrier in the contact reaction between the component (A) and the component (B). A coexisting method or the like can be used.
In the above reactions (4), (5) and (6), the component (C) may be added.

The loading of at least one of component (A) and component (B) on component (D) can be carried out in an inert hydrocarbon solvent. Specifically, benzene, toluene,
Aromatic hydrocarbons such as xylene and the like, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, and alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used. Among these, aromatic hydrocarbon solvents are preferred. The temperature at the time of contact is usually -50 to 200C, preferably -20 to 100C, more preferably 0 to 50C.
It is. The contact time is about 3 minutes to 200 hours, preferably about 12 minutes to 20 hours.

Next, a method for producing the polyolefin of the present invention using the catalyst of the present invention will be described. By using the catalyst of the present invention, homopolymerization of ethylene and copolymerization of ethylene with another α-olefin can be carried out.
Examples of the α-olefin used in the copolymerization include propylene, 1-butene, 1-pentene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, cyclopentene, cyclopentadiene, and butadiene. , 1,5-hexadiene, 1,4-hexadiene,
Examples include olefins such as 1,4-pentadiene, cyclic olefins, and dienes. These two or more comonomers can be mixed and used for copolymerization with ethylene.

The polymerization method using the catalyst of the present invention can be any of solution polymerization, slurry polymerization, and gas phase polymerization. Preferably, it is slurry polymerization or gas phase polymerization. Also, multi-stage polymerization is possible. Alternatively, it is possible to prepolymerize the olefin. The amount of the polymerization catalyst used in the method for producing a polyolefin according to the present invention, expressed by the concentration of the transition metal compound in the polymerization reaction system,
Usually, 10 ^-8 to 10 ^-2 mol / l, preferably 10 ^-7
It is desirably in the range of 10 to 10 ^-3 mol / l. The olefin pressure of the reaction system is not particularly limited, but preferably,
The range is from normal pressure to 50 kg / cm ² · G. The polymerization temperature is not limited, but is preferably from -30 ° C to 200 ° C.
, More preferably in the range of 0 ° C to 120 ° C. Particularly, the range of 50 to 90 ° C. is preferable. In the polymerization reaction, the molecular weight can be adjusted by known means, for example, by selecting a temperature or introducing hydrogen.

[0047]

Next, the present invention will be specifically described with reference examples, examples and comparative examples. The analytical instruments used for measuring the physical properties of the polyolefin are as follows. NMR was measured at 30 ° C. in deuterated chloroform using JEOL Ltd. (EX-400). MFR (Melt flow rate)
According to JIS K-6760, was measured at a temperature of 190 ° C. under a load of 2.16 kg, and HLMFR (high load melt flow rate) was measured under a condition of a load of 21.6 kg. The weight average molecular weight (Mw) is GPC (Waters 150C, column:
shodex).

Reference Example 1: Preparation of aluminoxane 50 ml of dry toluene was added to a 200 ml flask sufficiently purged with nitrogen, and Al ₂ (SO ₄ ) ₃ .14H ₂ O was added thereto.
(2.5 g) were suspended. After cooling to −20 ° C., 30 mmol of trimethylaluminum (1.11 mol / l toluene solution, 27 ml) was added over 15 minutes, and the mixture was heated to 80 ° C. and stirred for 7 hours. Thereafter, the aluminum sulfate compound was removed under a nitrogen atmosphere, and 70 ml of a 0.35 mol / l aluminoxane toluene suspension was recovered.

Reference Example 2 Loading of Aluminoxane on Carrier Toluene 25 was placed in a 100 ml flask which was sufficiently purged with nitrogen.
ml and silica (1.5 g of Davison 955 calcined at 300 ° C. for 4 hours) were added thereto, and the above-mentioned methylaluminoxane (0.35 M (in terms of Al atom) toluene solution,
(Methyl group / aluminum atom = 1.32) 37 ml was added,
The mixture was stirred at room temperature for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure. Heptane (50 ml) was added, and the mixture was stirred at 80 ° C. for 4 hours. Thereafter, washing was performed twice with heptane at 80 ° C. to obtain an aluminoxane-supported solid component. 33% by weight of the obtained solid component was aluminoxane. Finally, hexane was added to obtain a hexane suspension (45 mg / ml) of an aluminoxane-supported solid component.

Example 1: (Pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato)
Synthesis of zirconium dichloride Under an argon atmosphere, N, N'-diphenylformamidine (2.34 g, 11.9 mmol) was charged into a 100 ml container and dissolved in toluene (30 ml). 1.6M normal butyl lithium hexane solution (11.9mm
After l) was slowly added dropwise under ice-cooling, the mixture was stirred at room temperature for 3 hours to obtain a toluene solution of lithium-N, N'-diphenylformamidinato. Under an argon atmosphere, pentamethylcyclopentadienyl zirconium trichloride (11.9 mmol) was charged into a separately prepared 100 ml container, and dissolved in toluene (50 ml). The whole amount of the toluene solution of lithium-N, N'-diphenylformamidinate was added to this at room temperature, and the mixture was stirred at room temperature for 2 hours and at 60 ° C for 1 hour. After insoluble components in the reaction solution were separated by centrifugation, the reaction solution was concentrated to 30 ml and left in a freezer. The desired product was obtained as yellow crystals. ¹ H-NMR (CDCl ₃ ): δ (ppm) 8.77 (s, 1H), 7.35-7.1
1 (m, 10H), 2.09 (s, 15H); ¹³ C-NMR (CDCl ₃ ): δ (ppm) 159.1, 145.9, 129.
2, 127.3, 124.1, 120.7, 12.7.

Example 2: (pentamethylcyclopentadienyl) (N, N'-diphenylacetamidinato)
Synthesis of Zirconium Dichloride N, N'-diphenylacetamidine (2.10 g, 9.99 mmol) was charged into a 100 ml container under an argon atmosphere, and dissolved in toluene (50 ml). 1.6M normal butyllithium hexane solution (9.99mm
After l) was slowly added dropwise under ice-cooling, the mixture was stirred at room temperature for 3 hours to obtain a toluene solution of lithium-N, N'-diphenylacetamidinato. Under an argon atmosphere, pentamethylcyclopentadienyl zirconium trichloride (9.99 mmol) was charged into a separately prepared 100 ml container, and dissolved in toluene (50 ml). The whole amount of the toluene solution of lithium-N, N'-diphenylacetamidinate was added to this at room temperature, and the mixture was stirred at room temperature for 2 hours and at 60 ° C for 1 hour. After insoluble components in the reaction solution were separated by centrifugation, the reaction solution was concentrated to 30 ml and left in a freezer. The desired product was obtained as yellow crystals. ¹ H-NMR (CDCl ₃ ): δ (ppm) 7.34-7.13 (m, 10H), 2.
05 (s, 15H), 1.83 (s, 3H).

Example 3 Polymerization of Ethylene 1.5 liters (L) of SUS with sufficient nitrogen replacement
1.6 ml of a hexane solution of butylethylmagnesium (500 mmol / l) and 800 ml of isobutane were charged into an autoclave made from the above, and the temperature was raised to 70 ° C. with stirring. After applying an ethylene partial pressure of 10 kg / cm ² , 1.5 ml of a hexane suspension (45 mg / ml) of the solid component supporting aluminoxane of Reference Example 2 and (pentamethylcyclopentadienyl) (N, N′-diphenylforma) were added. Midinato) zirconium dichloride in toluene solution (1.0
(mmol / l) and 2 ml of the mixed solution contacted for 1 minute to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure of ethylene in the autoclave became constant at 10 kg / cm ² . After polymerization was performed at 70 ° C. for 30 minutes, the polymerization was stopped by purging. This result 41g
Of polyethylene was obtained. Activity per complex is 4100g
-Polyethylene / mmol-complex · hr · atm. M of this polyethylene at 190 ° C under a load of 2.16 kg
FR could not be measured because no outflow of polyethylene could be observed. The weight average molecular weight by GPC is Mw =
3,520,000.

Example 4: Polymerization of ethylene (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) Instead of zirconium dichloride, (pentamethylcyclopentadienyl)
Polymerization was carried out in the same manner as in Example 3, except that (N, N'-diphenylacetamidinato) zirconium dichloride was used. As a result, 65 g of polyethylene was obtained. Activity per complex is 6500g-polyethylene / mmo
l-complex · hr · atm. The MFR of this polyethylene at 190 ° C. under a load of 2.16 kg could not be measured because no outflow of polyethylene could be observed. GPC
Weight average molecular weight was Mw = 3,300,000.

Example 5: Polymerization of ethylene (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) Instead of zirconium dichloride, (pentamethylcyclopentadienyl)
Polymerization was carried out in the same manner as in Example 3, except that (N, N'-diphenylacetamidinato) zirconium dichloride was used and the amount of a hexane suspension (45 mg / ml) of the solid component supporting aluminoxane was changed to 4.6 ml. did. As a result, 99 g of polyethylene was obtained. The activity per complex is 9900 g-polyethylene / mmol-complex.hr.at
m. 190 ℃ of this polyethylene, load 2.16k
The MFR in g could not be measured because no outflow of polyethylene could be observed. The weight average molecular weight by GPC was Mw = 3,220,000.

Comparative Example 1 Polymerization of Ethylene (Pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) Instead of zirconium dichloride, (pentamethylcyclopentadienyl)
The same as Example 3 except that (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride was used and the amount of a hexane suspension (45 mg / ml) of the solid component carrying aluminoxane was changed to 3.1 ml. Polymerization was performed. As a result, 19 g of polyethylene was obtained. The activity per complex was 1900 g-polyethylene / mmol-complex.hr.atm. 190 of this polyethylene
The MFR at 2.degree. C. and a load of 2.16 kg could not be measured because no outflow of polyethylene could be observed.

Comparative Example 2: Polymerization of ethylene Bis (cyclopentadienyl) zirconium dichloride was used in place of (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) zirconium dichloride, and an aluminoxane-supported solid was used. Polymerization was carried out in the same manner as in Example 3 except that the amount of the hexane suspension solution (45 mg / ml) of the component was changed to 3.1 ml. As a result, 30 g of polyethylene was obtained. The activity per complex is
3000g-polyethylene / mmol-complex ・ hr ・ atm
Met. 190 ° C, 2.16 kg load of this polyethylene
Was 0.9 g / 10 min. The weight average molecular weight by GPC was Mw = 260,000.

Example 6: Polymerization of ethylene (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) Instead of zirconium dichloride, (pentamethylcyclopentadienyl)
(N, N'-diphenylacetamidinato) zirconium dichloride and the same procedure as in Example 3 except that a mixed gas of hydrogen and ethylene (hydrogen / ethylene: weight ratio 8 × 10 ⁻⁵ wt%) was used. Polymerization was performed. 40 g of this result
Of polyethylene was obtained. 4000g activity per complex
-Polyethylene / mmol-complex · hr · atm. M of this polyethylene at 190 ° C under a load of 2.16 kg
FR is 0.02g / 10min, HL at 21.6kg load
The MFR was 0.47 g / 10 minutes. The weight average molecular weight by GPC was Mw = 460,000.

Example 7: Polymerization of ethylene (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) Instead of zirconium dichloride, (pentamethylcyclopentadienyl)
(N, N'-diphenylacetamidinato) zirconium dichloride and the same procedure as in Example 3 except that a mixed gas of hydrogen and ethylene (hydrogen / ethylene: weight ratio 5 × 10 ⁻⁴ wt%) was used. Polymerization was performed. This result 28g
Of polyethylene was obtained. 2800g activity per complex
-Polyethylene / mmol-complex · hr · atm. M of this polyethylene at 190 ° C under a load of 2.16 kg
FR is 1.5g / 10min, HL at 21.6kg load
The MFR was 34.2 g / 10 minutes. The weight average molecular weight by GPC was Mw = 120,000.

Comparative Example 3: Polymerization of ethylene Bis (cyclopentadienyl) zirconium dichloride was used in place of (pentamethylcyclopentadienyl) (N, N'-diphenylformamidinato) zirconium dichloride, and a solid component supported on aluminoxane was used. The volume of the hexane suspension solution (45 mg / ml) was 3.1 ml,
Mixed gas of hydrogen and ethylene (hydrogen / ethylene: weight ratio 1)
Polymerization was carried out in the same manner as in Example 3 except that (× 10 ⁻⁴ wt%) was used. As a result, 68 g of polyethylene was obtained. The activity per complex is 6800 g-polyethylene / mmo
l-complex · hr · atm. The MFR of this polyethylene at 190 ° C. under a load of 2.16 kg was 11 g / 10 minutes, and the HLMFR under a load of 21.6 kg was 222 g / 1.
It was 0 minutes. The weight average molecular weight by GPC is Mw =
82,000.

The results of Examples 3 to 7 and Comparative Examples 1 to 3 are shown in a table.

[0061]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a flowchart of catalyst preparation in the method for producing an ethylene polymer of the present invention.

Claims (7)

[Claims] 1. A compound represented by the general formula (1): (L) _m (Cp) _n MX ¹ X ² (1) wherein M is a transition metal of Group 4 of the periodic table, and L is Equation (2) Wherein R ¹ and R ² may be the same or different and are aryl or substituted aryl groups; A and B may be the same or different; each is an atom of Group 15 of the periodic table; Is an atom of group 14 of the periodic table, A is bonded to M, B is coordinated by a lone pair of electrons, or when M, A, D and B are in resonance. Are bonded by resonance, R ³ is a hydrogen atom, an aliphatic hydrocarbon group, or a hetero atom-containing hydrocarbon group, and R ³ may be bridged with R ¹ or R ^2. Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group, and m is 1 or 2. , N is 1 when m is 1, and m is 2 Is 0 when m
When is 1, it may be cross-linked between the L group and the Cp group, when m is 2, it may be cross-linked between the L group and the L group, and X ¹ and X ² are the same And may be different, each being a hydrogen atom, a halogen atom, an organic metalloid group, an alkoxy group, an amino group, a hydrocarbon group, or a hetero atom-containing hydrocarbon group. ] The catalyst component for olefin polymerization which consists of a transition metal compound (A) shown by these. 2. The transition metal compound (A) according to claim 1, wherein R ³ is a hydrogen atom or a linear hydrocarbon having 1 to 10 carbon atoms in the general formula (2).
3. The catalyst component for olefin polymerization according to item 1. 3. The general formula (1) according to claim 1 or 2.
And a compound (B-2) that reacts with the organoaluminum oxy compound (B-1) and the transition metal compound represented by the general formula (1) to form an ion pair. An olefin polymerization catalyst comprising at least one compound (B) selected from the group. 4. The general formula (1) according to claim 1 or 2
And a compound (B-2) that reacts with the organoaluminum oxy compound (B-1) and the transition metal compound represented by the general formula (1) to form an ion pair. An olefin polymerization catalyst comprising at least one compound (B) selected from the group and at least one compound (C) selected from organic lithium, organic magnesium, and organic aluminum. 5. The general formula (1) according to claim 1 or 2
And a compound (B-2) that reacts with the organoaluminum oxy compound (B-1) and the transition metal compound represented by the general formula (1) to form an ion pair. An olefin polymerization catalyst comprising at least one compound (B) selected from the group and a carrier (D). 6. The general formula (1) according to claim 1 or 2.
And a compound (B-2) that reacts with the organoaluminum oxy compound (B-1) and the transition metal compound represented by the general formula (1) to form an ion pair. An olefin polymerization catalyst comprising: at least one compound (B) selected from the group; at least one compound (C) selected from organolithium, organomagnesium, and organoaluminum; and a carrier (D). 7. A method for producing a polyolefin, comprising using the catalyst according to claim 3. Description: