JPH11236408A - Catalyst for olefin polymerization and production of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst capable of forming a polyolefin having a high molecular weight in high activity by allowing a carrier to carry a specific amidine derivative and an organic aluminum hydroxy compound or the like. SOLUTION: This catalyst is obtained by allowing (C) a carrier to carry (A) an amidine derivative of a transition metal compound preferably of formula I [M is a group IV transition metal in the periodic table; L is formula II (R<1> and R<2> are each a hydrocarbon, an alkylsilyl or the like; A and B are each a group XV atom, 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, a halogen 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, (m) is 0; X<1> and X<2> are each H, a halogen, an organic metalloid or the like], and (B) at least one kind of compound selected from (i) an organic aluminum hydroxy compound, and (ii) a compound capable of forming an ion pair by reacting with the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel catalyst for olefin polymerization and a method for producing a polyolefin. More specifically, the present invention relates to an olefin polymerization catalyst capable of obtaining a polyolefin having a high activity and a high molecular weight, and a method for producing a 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 have reported olefin polymerization catalysts comprising various metallocene compounds and linear or cyclic organoaluminum oxy compounds. However, in the biscyclopentadienyl complex system used in these conventional techniques, a high-molecular-weight polyolefin cannot be obtained when polymerization is performed 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 Although it is described that a high molecular weight polyolefin can be obtained by polymerization using dichloride, it cannot be used for industrial production due to low polymerization activity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst system capable of efficiently producing an industrial process, producing a highly active and high molecular weight polyolefin at a reaction temperature of about 50 ° C. or higher.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific amidine derivative (A) reacts with an organic aluminum oxy compound (B-1) and the amidine derivative to form an ion pair. It has been found that a catalyst in which at least one compound (B) selected from the group consisting of the compounds (B-2) forming a compound is supported on a carrier (D) satisfies the object, and arrived at the present invention. That is, the present invention provides the following olefin polymerization catalyst and a method for producing a polyolefin.

1) An amidine derivative (A) having a transition metal belonging to Group 4 of the periodic table, an organoaluminum oxy compound (B-1) and a compound (B) which reacts with the amidine derivative (A) to form an ion pair -2) at least one compound (B) selected from the group consisting of and a carrier (D), wherein the amidine derivative (A) and the compound (B) are supported on the carrier (D). Olefin polymerization catalyst. 2) The amidine derivative (A) has 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 a compound of the formula (2) (Wherein, R ¹ and R ² may be the same or different, each being a hydrocarbon group, an alkylsilyl group, or an alkylgermyl group; A and B may be the same or different; And D is an atom of group 14;
A is bound to M, B is coordinated by a lone pair or, if resonating between M, A, D and B, is bound by the resonance; R ³ is Hydrogen atom,
It is a halogen atom, an organic metalloid group, an alkoxy group, an amino group, a hydrocarbon group, or a hetero atom-containing hydrocarbon group. Wherein 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; Is 1 when m is 1 and is 0 when m is 2, when m is 1, a bridge may be formed between the L group and the Cp group, and when m is 2, May be cross-linked between the group and the L group,
X ¹ and X ² may be the same or different and are each 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 olefin polymerization catalyst according to the above 1, which is a transition metal compound represented by the formula: 3) The catalyst for olefin polymerization according to 1 or 2 above, which contains at least one kind of organometallic compound (C) selected from organolithium, organomagnesium, and organoaluminum. 4) A method for producing a polyolefin, comprising using the catalyst according to any one of the above items 1 to 3.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst according to the present invention and a method for producing a polyolefin using the catalyst will be specifically described below. The fourth component of the catalyst component (A) of the present invention
The amidine derivative of a Group 4 transition metal refers to various amidine derivative compounds containing a Group 4 transition metal of the periodic table, and among them, a transition metal compound represented by the following general formula (1) is preferably used.

Embedded image (L) _m (Cp) _n MX ¹ X ² (1) wherein the symbols have the same meanings as described above. In the above formula, transition metals belonging to Group 4 of the periodic table represented by M are titanium, zirconium, and hafnium. In the group of L (general formula (2)), the hydrocarbon group represented by R ¹ and R ² is
Examples thereof include alkyl, alkenyl, aryl, substituted aryl, and arylalkyl having 1 to 20 carbon atoms.

In the present invention, it is preferable that R ¹ and R ² are an aryl group or a substituted aryl group in order to obtain a highly active and high molecular weight polyolefin. Examples of the substituent of the aryl group include a halogen atom and an alkyl group. Preferred R ¹ and R ² are a phenyl group, a fluorophenyl group, a trifluorophenyl group,
Examples thereof include a methylphenyl group, a 2,6-dimethylphenyl group, a naphthalenyl group, a fluoronaphthalenyl group, and an anthracenyl group. R ³ is preferably a hydrogen atom, an alkyl group, an aryl group or a substituted aryl group.

In the transition metal compound represented by the general formula (1), when M is zirconium, a specific compound is (pentamethylcyclopentadienyl)
(N, N'-bis (phenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl)
(N, N′-bis (phenyl) benzamidinato) zirconium dichloride, (normal propylcyclopentadienyl) (N, N′-bis (phenyl) benzamidinato) zirconium dichloride, (normal butylcyclopentadienyl) Enyl) (N, N'-bis (phenyl)
Benzamidina zirconium dichloride, (indenyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, (trimethylindenyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, (Pentamethylcyclopentadienyl) (N, N'-bis (fluorophenyl)
(Benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N'-bis (trifluoromethylphenyl) benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N ' -Bis (2,6-dimethylphenyl)
(Benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N′-bis (naphthalenibenzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N ′)
-Bis (fluoronaphthalenyl) benzamidinato)
Zirconium dichloride, (cyclopentadienyl)
(N, N'-bis (naphthalenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N'-bis (fluoronaphthalenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) ) (N, N'-bis (anthracenyl) benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N'-bis (anthracenyl) benzamidinato) zirconium dichloride, bis (N, N '-Bis (phenyl) benzamidinato) zirconium dichloride, bis (N, N'-bis (naphthalenyl) benzamidinato) zirconium dichloride, bis (N, N'-bis (anthracenyl) benzamidinato) zirconium Dichloride, bis (N, N'-bis (fluorophenyl Benzamidinato) zirconium dichloride, bis (N, N'-bis (methylphenyl) benzamidinato) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride , Dimethylsilylene (tetramethylcyclopentadienyl) (N, N'-bis (phenyl)
Amidinato) zirconium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (N, N'-
Bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (indenyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride,
Bis (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, dimethylsilylenebis (N, N'-bis (phenyl) amidinato) zirconium dichloride, isopropylidenebis (N, N'-bis (phenyl) Amidinato) zirconium dichloride and the like.

Preferably, (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, bis (N, N'-bis (phenyl) benzamidinato) zirconium dichloride It is. The general formula (1) in which the Group 4 transition metal M that can be used in the present invention is hafnium and titanium.
Examples of the transition metal compound include those obtained by substituting zirconium with hafnium or titanium in the specific examples of the above zirconium compound.

Component (B-1) used in the present invention
As the organic aluminum oxy compound, an aluminoxane compound is usually preferably used. A typical example of the above aluminoxane is an organoaluminum compound represented by the general formula (3) or (4).

[0012]

In the formula, R ⁴ is a hydrogen atom, 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 and an isobutyl group, and a methyl group and an isobutyl group are preferable. However, a plurality of R ⁴ in the same formula may be the same or different. That is, a substituent such as a different hydrocarbon group may be arbitrarily contained, and for example, a repeating unit having a different hydrocarbon group may be bonded in a block manner, or may be bonded regularly or irregularly. May be done. 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). And a method in which solid, liquid or gaseous water is allowed to act on an organoaluminum compound in a hydrocarbon solvent. In this case, two kinds of the compounds of the general formulas (3) and (4) are used as the aluminoxane,
Alternatively, a mixture of more than these may be used.

The organoaluminum compound used for producing aluminoxane includes trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trinormalbutylaluminum, triisobutylaluminum,
sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trialkylaluminum such as tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dialkylaluminum halide such as diisobutylaluminum chloride, It is selected from dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum methoxide, and dialkylaluminum aryloxides such as diethylaluminum phenoxide. Among them, it is preferable to be selected from trialkylaluminums, particularly trimethylaluminum and triisobutylaluminum.

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.

Amidine derivative (A) used in the present invention
Examples of the at least one compound (B-2) selected from the group consisting of compounds that form an ion pair by reacting with a compound described in JP-A-1-501950, JP-A-1-502036, and -
179005 JP, JP-A-3-179006, JP-A-3-207703
And ionic compounds and carborane compounds described in Japanese Patent Application Laid-Open No. Hei. 3-207704 and JP-A-3-207704.

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.

The compound (B-2) which forms an ion pair by reacting with the amidine derivative (A) as described above can be used as a mixture of two or more kinds. Further, a borate compound which is reactive with a carrier as shown in WO96 / 41808 may be used.

The carrier (D) according to the present invention is a porous fine-particle carrier, which is preferably solid in a polymerization medium, and may be an inorganic oxide, an inorganic chloride, an inorganic carbonate, an inorganic sulfate, or an organic material. Selected from polymers. As the inorganic oxide, for example, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , Ti
O ₂ , CaO inorganic oxide or SiO ₂ —Al ₂ O ₃ ,
_{SiO 2 -MgO, SiO 2 -ZrO 2} , SiO 2 -TiO
₂ , SiO ₂ —CaO, Al ₂ O ₃ —MgO, Al ₂ O ₃ —Z
rO ₂ , Al ₂ O ₃ —TiO ₂ , Al ₂ O ₃ —CaO, ZrO
_2- TiO ₂ , ZrO ₂ -CaO, ZrO ₂ -MgO, Ti
Examples thereof include complex oxides such as O ₂ -MgO, inorganic chlorides such as magnesium chloride, inorganic carbonates such as magnesium carbonate, calcium carbonate, and strontium carbonate, and inorganic sulfates such as magnesium sulfate, calcium sulfate, and barium sulfate. Examples of the organic polymer carrier include fine particles such as polyethylene, polypropylene, and polystyrene. Among these, it is desirable to be selected from inorganic oxides, especially SiO ₂ , Al ₂ O ₃ and their composite oxides.

The porous fine particles according to the present invention have an average particle diameter of 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. The specific surface area is 1
It is preferably in the range of 0 to 1000 m ² / g.
It is preferably in the range of 00 to 800 m ² / g, particularly preferably in the range of 200 to 600 m ² / g.
As for the pore volume is preferably in the range of 0.3~3cm ³ / g, preferably in the range of more 0.5~2.5cm ³ / g, particularly preferably, 1.0～2.0Cm ³
/ G range.

The preferred carrier according to the present invention is Si
O ₂ , Al ₂ O ₃ and their composite oxides have different amounts of adsorbed water and surface hydroxyl groups depending on the treatment conditions. These preferred ranges include a water content of 5% by weight.
And the amount of surface hydroxyl groups is 1 / (n
m) ² or more. The water content and the amount of surface hydroxyl groups can be controlled by selecting the firing temperature and the firing time, and by treating with an organic aluminum compound, an organic boron compound, or the like.

In the polyolefin polymerization catalyst according to the present invention, the use ratio of component (A) to component (B) is preferably 1: 1 to 1 in the case of component (B-1).
The ratio is preferably 1: 10000, more preferably 1:10 to 1: 1000. In the case of the component (B-2), the molar ratio is preferably 10: 1 to 1: 100, more preferably 2: 1 to 1: 1.
A range of 1:10 is desirable.

The use ratio of the component (B) and the carrier (D) in the olefin polymerization catalyst according to the present invention depends on the component (B-
In the case of 1), the weight ratio is preferably 1: 0.5 to 1: 1.
00, more preferably in the range of 1: 1 to 1:10. In the case of the component (B-2), the weight ratio is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 10
A range of 0 is desirable. The ratio of the component (A) to the carrier (D) used is preferably from 1: 5 to 1: 1000 by weight.
0, more preferably in the range of 1:10 to 1: 500.

The contact method according to the present invention comprises: (1) component (B)
(2) a method in which the component (A) is supported on the carrier (D) after the component (A) is supported on the carrier (D) after the component (A) is brought into contact with the component (A); It is desirable to select from a method of loading the component (A) on the carrier (D) and then loading the component (B). In particular, the methods (1) and (2) are desirable, and the method (2) is most desirable.

The contact of each catalyst component according to the present invention is carried out by contacting an aromatic hydrocarbon such as benzene, toluene and xylene, butane,
It is desirable to carry out the reaction in an aliphatic hydrocarbon such as isobutane, pentane, hexane, heptane, octane and decane, and an alicyclic hydrocarbon such as cyclopentane and cyclohexane. In the case of the method (1) or (3), it is preferable to use an aromatic hydrocarbon. In the case of the method (2), when the component (B) is supported on the carrier (D), it is preferable to use an aromatic hydrocarbon, but when the component (A) is supported, the component (A) is preferably an aliphatic hydrocarbon. If it is soluble in hydrocarbons, it is industrially advantageous to use aliphatic hydrocarbons. The temperature at the time of contact is -70 ° C to 200 ° C, preferably -20 ° C to 12 ° C.
The temperature is 0 ° C., and the contact time in each step is preferably 10 minutes to 10 hours.

In the present invention, it is important that each component, particularly component (A), is supported on the carrier (D). Therefore, it is desirable to remove the solvent from the catalyst component by filtering or distilling off the solvent after bringing each component into contact with the carrier.

The at least one organometallic compound (C) selected from organolithium, organomagnesium and organoaluminum used in the olefin polymerization catalyst according to the present invention is specifically exemplified below.

As the organic lithium, methyl lithium,
It is selected from ethyl lithium, normal propyl lithium, normal butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, normal pentyl lithium, isopentyl lithium, and neopentyl lithium. Among them, normal butyl lithium,
Tert-butyllithium is preferred.

As the organic magnesium, normal butyl ethyl magnesium, di-sec-butyl magnesium, normal butyl-sec-butyl magnesium,
It is selected from di-tert-butylmagnesium, dineopentylmagnesium, and dinormalhexylmagnesium. Among them, normal butyl ethyl magnesium,
Di-sec-butylmagnesium and dinormalhexylmagnesium are preferred.

Further, as the organic aluminum, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, tri-sec-butyl aluminum, tri-tert aluminum
-Butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum,
Selected from among tricyclohexyl aluminum. Of these, trimethyl aluminum and triisobutyl aluminum are preferred. The component (C) as described above is
Two or more kinds can be used in combination.

The use ratio of component (A) to component (C) is preferably in the range of 1:10 to 1: 100,000, more preferably 1: 100 to 1: 10000 in terms of molar ratio. By using the method of the present invention, homopolymerization of ethylene and copolymerization with other α-olefins can be carried out, but α-olefins used in the copolymerization are propylene, 1-butene, -Pentene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, cyclopentene, cyclopentadiene, butadiene, 1,5
Examples thereof include olefins such as hexadiene, 1,4-hexadiene and 1,4-pentadiene, cyclic olefins, and dienes. These two or more comonomers can be mixed and used for copolymerization with ethylene.

The polymerization method used in 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 is usually from 10 ^-8 to 1, expressed as the concentration of the transition metal compound in the polymerization reaction system.
0 ^-2 mol / l, preferably 10 ^-7 to 10 ^-3 mol /
It is desirably in the range of l. The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 50 kg.
/ Cm ² G and the polymerization temperature is not limited,
Preferably, it is in the range of −30 ° C. to 200 ° C. Particularly preferably, it is in the range of 0 ° C to 120 ° C. More preferably, it is 50 to 90 ° C. The molecular weight at the time of polymerization can be adjusted by known means, for example, by selecting a temperature or introducing hydrogen.

[0037]

Next, the present invention will be described specifically with reference to examples. The analytical instruments used for measuring the physical properties are as follows. NMR was measured at 30 ° C. in deuterated chloroform using a JEOL EX-400 machine. MFR (melt flow rate) is measured at a temperature of 19 according to JIS K-6760.
The measurement was performed at 0 ° C. and a load of 2.16 kg, and the HLMFR (high load melt flow rate) was measured at a load of 21.6 kg. The MT was measured using a polymer powder as a measurement sample, using an MT measuring device manufactured by Toyo Seiki Seisaku-sho, and measuring the resin temperature at 190.
° C, extrusion speed 15mm / min, winding speed 6.5m /
The measurement was performed under the conditions of a nozzle diameter of 2.095 mm and a nozzle length of 8 mm. The molecular weight (Mn, Mw, Mz) and molecular weight distribution (Mw / Mn, Mz / Mw) were determined by GPC (Waters 15
0C, column shodex).

Reference Example 1: Loading of Aluminoxane on Carrier Toluene was placed in a 200 ml flask sufficiently purged with nitrogen.
ml and silica (Crosfield ES-70 40
3.0 g of the mixture was calcined at 0 ° C. for 8 hours, and methylaluminoxane (PMAO, manufactured by Tosoh Akzo Co., Ltd.) was added to the suspension.
0.37mol / l (Al atom conversion) toluene solution) 72m
was added and the mixture was stirred at room temperature for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure to obtain a solid component. 33 wt% of the obtained solid component was aluminoxane.

Reference Example 2: Synthesis of (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride 1.1 g of diphenylbenzamidine was placed in a 100 ml container sufficiently purged with argon. (4 mmol) was added and dissolved with 50 ml of dry toluene. 2.5 ml of normal butyllithium (1.6 mol / l hexane solution) was slowly added dropwise thereto under ice-cooling, followed by stirring at room temperature for 3 hours.
A toluene solution of N, N'-bis (phenyl) benzamidinato was obtained. 200ml sufficiently purged with argon
Was prepared separately, and pentamethylcyclopentadienyl zirconium trichloride 1.3 g (4 mmo) was prepared.
l) was added and dissolved with 50 ml of dry toluene. The whole amount of the above-mentioned toluene solution of lithium-N, N'-bis (phenyl) benzamidinato was added to this at room temperature, and the mixture was stirred for 5 hours. Then, insoluble components in the reaction solution were separated by centrifugation. . After concentrating the solution portion to a volume of 15 ml, 7 ml of dry hexane was added, and
By leaving it for 0 hour, 1.6 g of the desired (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride was obtained as pale yellow crystals (yield 70%). ¹ H-NMR (CDCl ₃ ): δ 7.14-6.89 (15H, m, arom.H),
2.14 (15H, s, Me).

Reference Example 3: Synthesis of (pentamethylcyclopentadienyl) (N, N'-bis (2,6-dimethylphenyl) benzamidinato) zirconium dichloride In a 100 ml container sufficiently purged with argon, 1.6 g of bis (2,6-dimethylphenyl) benzamidine
(5 mmol) was added and dissolved with 50 ml of dry toluene. To this, normal butyl lithium (1.6 mol / l
Hexane solution (3.0 ml) was slowly added dropwise under ice-cooling, and the mixture was stirred at room temperature for 3 hours, and lithium-N, N′-bis (2,6
A solution of (dimethylphenyl) benzamidinato in toluene was obtained. A 200-ml container sufficiently purged with argon was separately prepared, and 1.6 g (5 mmol) of pentamethylcyclopentadienyl zirconium trichloride was added thereto and dissolved in 50 ml of dry toluene. To this, lithium-N, N'-bis (2,6-dimethylphenyl)
The whole amount of the benzamidinato toluene solution was added at room temperature, and the mixture was stirred for 5 hours. Then, insoluble components in the reaction solution were separated by centrifugation. The solution was concentrated to a volume of 15 ml, and 7 ml of dry hexane was added.
By leaving at 0 ° C. for 8 hours, 1.3 g of the objective (pentamethylcyclopentadienyl) (N, N′-bis (2,6-dimethylphenyl) benzamidinato) zirconium dichloride was obtained as pale yellow crystals. . ¹ H-NMR (CDCl ₃ ): δ 7.10-6.80 (11H, m, arom.H),
2.22 (12H, s, Ph- Me ), 2.03 (15H, s, Cp- Me ).

Reference Example 4: Synthesis of (pentamethylcyclopentadienyl) (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride Bis (trimethylsilyl) benzamidine was placed in a 100 ml container sufficiently purged with argon. 1.3g (5mmo
l) was added and dissolved with 50 ml of dry toluene. 3.1 ml of normal butyllithium (1.6 mol / l hexane solution) was slowly added dropwise thereto under ice-cooling, followed by stirring at room temperature for 3 hours to obtain a solution of lithium-N, N'-bis (trimethylsilyl) benzamidinato in toluene. I got A 200-ml container sufficiently purged with argon was separately prepared, and 1.6 g (5 mmol) of pentamethylcyclopentadienyl zirconium trichloride was added thereto and dissolved in 50 ml of dry toluene. The lithium-N, N '
The whole amount of the toluene solution of -bis (trimethylsilyl) benzamidinato was added at room temperature, and the mixture was stirred for 5 hours. Then, insoluble components in the reaction solution were separated by centrifugation. After the solution portion was concentrated to a volume of 15 ml, 7 ml of dry hexane was added, and the mixture was allowed to stand at -20 ° C. for 8 hours to obtain the desired (pentamethylcyclopentadienyl) (N,
N'-bis (trimethylsilyl) benzamidinato)
1.5 g of zirconium dichloride was obtained as pale yellow crystals. ¹ H-NMR (CDCl ₃ ): δ 7.41-7.08 (5H, m, arom.H),
2.22 (15H, s, Cp- Me ), -0.10 (18H, s, Si- Me ).

Reference Example 5: Synthesis of (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) methylamidinato) zirconium dichloride 2.1 g of diphenylmethylamidine was placed in a 100 ml container sufficiently purged with argon. (10 mmol) and dissolved in 50 ml of dry toluene. To this, 6.8 ml of normal butyl lithium (1.6 mol / l hexane solution) was slowly added dropwise under ice-cooling, followed by stirring at room temperature for 3 hours to obtain a toluene solution of lithium-N, N'-bis (phenyl) methylamidinate. I got 200m sufficiently purged with argon
1 container is separately prepared and 3.9 g of pentamethylcyclopentadienyl zirconium trichloride (12 mm
ol) and dissolved in 50 ml of dry toluene. The whole amount of the toluene solution of lithium-N, N'-bis (phenyl) methylamidinate was added to this at room temperature, and the mixture was stirred for 5 hours, and then the insoluble components in the reaction solution were separated by centrifugation. . After concentrating the solution portion to a volume of 15 ml, the solution was allowed to stand at −20 ° C. overnight to obtain the desired (pentamethylcyclopentadienyl) (N, N′-bis (phenyl) methylamidinato) zirconium dichloride. g were obtained as pale yellow crystals (yield 65%). ¹ H-NMR (CDCl ₃ ): δ 7.35-7.13 (10H, m, arom.H),
2.05 (15H, s, Me), 1.83 (15H, s, Me).

Example 1 Preparation of Catalyst Toluene was placed in a 200 ml flask which was sufficiently purged with nitrogen.
ml and 3.0 g of the supported aluminoxane prepared in Reference Example 1.
And 25 mg of (pentamethylcyclopentadienyl) (N, N′-bis (phenyl) benzamidinato) zirconium dichloride [component (A)] synthesized in Reference Example 2 was added to 10 ml of toluene. The dissolved solution was added, and the mixture was stirred at room temperature for 20 minutes. At this time, Al /
(A) = 400 (molar ratio). Thereafter, the solvent was distilled off under reduced pressure to obtain a solid component. Polymerization of ethylene A hexane solution of butylethylmagnesium (0.
After introducing 1.6 ml of 5 mol / l) and 800 ml of isobutane, the temperature was raised to 70 ° C. Next, ethylene was introduced so as to have a partial pressure of 10 kg / cm ² . The polymerization was started by injecting 330 mg of the solid component prepared above with nitrogen at a pressure of 40 kg / cm ² . Mixed gas pressure 10kg /
Polymerization was carried out at 70 ° C. for 30 minutes in cm ² to obtain 157 g of polyethylene. 190 ° C, load 2 of this polyethylene
The MFR at 1.6 kg (HLMFR) did not flow out and could not be measured.

Examples 2-3: Polymerization of ethylene The procedure of Example 1 was repeated except that the amount of component (A) used was changed as shown in Table 1. The results are shown in Table 1.

Comparative Example 1 Polymerization of Ethylene A hexane solution of butylethylmagnesium (0.1 mL) was placed in a 1.5 L SUS autoclave sufficiently purged with nitrogen.
(5 mol / l), 400 mg of the supported aluminoxane prepared in Reference Example 1, and 800 ml of isobutane were introduced, and the temperature was raised to 70 ° C. Next, ethylene was introduced so as to have a partial pressure of 10 kg / cm ² . (Pentamethylcyclopentadienyl) (N,
N′-bis (phenyl) benzamidinato) zirconium dichloride [component (A)] 10 mg
The polymerization was started by injecting 3.3 ml of the solution dissolved in ml with nitrogen at a pressure of 40 kg / cm ² . Mixed gas pressure 10
Polymerization was performed for 30 minutes at 70 ° C. and 30 kg / cm ² to obtain 34 g of polyethylene. The MFR (HLMFR) of the polyethylene at 190 ° C. under a load of 21.6 kg did not flow out and could not be measured.

Comparative Example 2 Polymerization of Ethylene A hexane solution of butylethylmagnesium (0.1%) was placed in a 1.5 L SUS autoclave sufficiently purged with nitrogen.
After introducing 1.6 ml of 5 mol / l) and 800 ml of isobutane, the temperature was raised to 70 ° C. Next, ethylene was introduced so as to have a partial pressure of 10 kg / cm ² . 3 m of toluene was added to 315 mg of the supported aluminoxane prepared in Reference Example 1.
10 mg of (pentamethylcyclopentadienyl) (N, N′-bis (phenyl) benzamidinato) zirconium dichloride [component (A)] prepared in Reference Example 2 in 10 ml of toluene. Was contacted at room temperature for 1 minute. Polymerization was started by injecting this contact material with nitrogen at a pressure of 40 kg / cm ² . Polymerization was performed at 70 ° C. for 30 minutes at a mixed gas pressure of 10 kg / cm ² to obtain 61 g of polyethylene. MFR (HLMF) of this polyethylene at 190 ° C. under a load of 21.6 kg
R) did not flow out and could not be measured.

Example 4: Polymerization of ethylene A hexane solution of butylethylmagnesium (0.5 mol)
/ L) Instead of 1.6 ml, hexane solution of butylethylmagnesium (0.5 mol / l) and hexane solution of triisobutylaluminum (TIBAL) (0.5 mol / l)
/ L), except that 1.6 ml of a mixed solution of 2/1 was used. The results are shown in Table 2.

Example 5: Polymerization of ethylene The procedure of Example 4 was repeated except that the amount of the component (A) used was changed as shown in Table 2. The results are shown in Table 2.

Examples 6 and 7: Polymerization of ethylene The same procedure as in Example 2 was carried out except that a hydrogen / ethylene mixed gas having the concentration shown in Table 2 was used instead of ethylene.
The results are shown in Table 2.

Example 8: Polymerization of ethylene A hexane solution of butylethylmagnesium (0.5 mol)
/ L) Instead of 1.6 ml, 1.6 ml of a hexane solution of trinormal butyl aluminum (0.5 mol / l) was used, and a hydrogen / ethylene mixed gas having a concentration shown in Table 2 was used in place of ethylene. Performed as in Example 2. The results are shown in Table 2.

Examples 9 to 11: Polymerization of ethylene As component (A), Table 3 was used in place of (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride. The procedure was performed in the same manner as in Example 2 except that the described compounds were used.
The results are shown in Table 3.

Example 12 Preparation of Catalyst A 200 ml flask sufficiently purged with nitrogen was charged with methylaluminoxane (PMAO, manufactured by Tosoh Akzo, 0.37 mol / l).
(Toluene solution in terms of Al atom) 72 ml, toluene 3
0 ml and (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride [component (A)] synthesized in Reference Example 2 49
A solution of mg in 10 ml of toluene was added, and the mixture was stirred at room temperature for 10 minutes. This solution is silica (calculated from Crossfield ES-70 at 400 ° C. for 8 hours).
The mixture was added to a suspension prepared by adding 30 ml of toluene to 3.0 g, and stirred at room temperature for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure to obtain a solid component. The obtained solid component is 33 w
t% is aluminoxane, Al / (A) = 200
(Molar ratio). Polymerization of ethylene A hexane solution of butylethylmagnesium (0.
After introducing 1.6 ml of 5 mol / l) and 800 ml of isobutane, the temperature was raised to 70 ° C. Next, ethylene was introduced so as to have a partial pressure of 10 kg / cm ² . The polymerization was started by injecting 290 mg of the solid component prepared above with nitrogen at a pressure of 40 kg / cm ² . Mixed gas pressure 10kg /
for 30 minutes of polymerization at cm ^2, 70 ℃, to obtain a polyethylene 167 g. 190 ° C, load 2 of this polyethylene
The MFR at 1.6 kg (HLMFR) did not flow out and could not be measured.

The results of the examples and comparative examples are summarized in a table.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a flowchart of the preparation of a catalyst used in the method of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shintaro Inazawa Oita Prefecture Oita City Oaza Nakanosu 2 Japan Polyolefin Co., Ltd. Oita Research Laboratory

Claims (4)

[Claims] 1. An amidine derivative (A) having a transition metal of Group 4 of the periodic table and an organoaluminum oxy compound (B)
-1) and at least one compound (B) selected from the group consisting of compounds (B-2) which react with the amidine derivative (A) to form an ion pair, and a carrier (D), An olefin polymerization catalyst, wherein the derivative (A) and the compound (B) are supported on a carrier (D). 2. The amidine derivative (A) is represented by the general formula (1): (L) _m (Cp) _n MX ¹ X ² (1) wherein M is a group 4 of the periodic table. L is a transition metal; (Wherein, R ¹ and R ² may be the same or different and are each a hydrocarbon group, an alkylsilyl group, or an alkylgermyl group; A and B may be the same or different; D is a group 14 atom, A is bonded to M, B is coordinated by a lone pair, or if M, A, D and B resonate, R ³ is a hydrogen atom, a halogen atom, an organic metalloid group,
It is an alkoxy group, an amino group, a hydrocarbon group, or a hetero atom-containing hydrocarbon group. 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; Is 1 when m is 1, 0 when m is 2, 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 for olefin polymerization according to claim 1, which is a transition metal compound represented by the formula: 3. The catalyst for olefin polymerization according to claim 1, which comprises at least one kind of an organometallic compound (C) selected from organolithium, organomagnesium and organoaluminum. 4. A method for producing a polyolefin, comprising using the catalyst according to claim 1.