JP4596951B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

  The present invention relates to a solid catalyst for olefin polymerization and an olefin polymerization method using the catalyst. Specifically, an olefin polymerization catalyst that can be applied to suspension polymerization (slurry polymerization) of olefins and gas phase polymerization, and can produce a polymer having excellent powder properties with very high production efficiency, In particular, the present invention provides a catalyst for ethylene polymerization, and relates to a method for polymerizing ethylene using the same.

Conventionally, a so-called Ziegler-Natta type catalyst composed of a titanium compound and an organoaluminum compound is known as a catalyst for producing an olefin polymer or copolymer. On the other hand, in recent years, ethylene homopolymerization or copolymerization of ethylene with other α-olefins, aluminoxane which is a kind of soluble halogen-containing transition metal compounds such as bis (cyclopentadienyl) zirconium dichloride and organoaluminum oxy compounds. A technique for polymerizing with high activity by using a catalyst consisting of the following has been found (see, for example, Patent Documents 1 and 2).
On the other hand, as a catalyst system using an activator other than the organoaluminum oxy compound, [Cp ₂ TiMe (THF)] ⁺ [B (Ph) ₄ ] ⁻ (Cp: cyclopentadienyl group, Me: methyl group, Ph : Phenyl group, THF: tetrahydrofuran), and the polymerization of ethylene has been reported (see Non-Patent Document 1). It has also been reported that a zirconium complex represented by [Cp ₂ ZrR (L)] ⁺ (R: methyl group or benzyl group, L: Lewis base) polymerizes ethylene (see Non-Patent Document 2).

Patent Document 3 and Patent Document 4 disclose a method of polymerizing an olefin using a catalyst comprising a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. ing.
In addition, a catalyst system using an organoaluminum compound and clay, clay mineral, ion-exchange layered compound or the like as an activator is disclosed in Patent Documents 5 to 8, and the like. However, the catalyst systems proposed in these conventional techniques are often soluble in the reaction system, and reflecting this, the olefin polymer obtained by slurry polymerization or gas phase polymerization has an irregular particle shape. In addition, there is a problem that the bulk density is small and there are a lot of fine powders and the particle properties are extremely bad, and the polymer adheres to the wall surface of the reactor, the stirring blades, etc. For this reason, the production process is usually limited to the solution polymerization method. However, in the solution polymerization method, when an attempt is made to produce a high molecular weight polymer, the viscosity of the solution containing the polymer becomes extremely high and the productivity is greatly increased. There is a problem of lowering, and it cannot be said that it is a preferable method in terms of cost, and there is a big problem in industrial application.

In order to solve the above problems, an attempt has been made to prepolymerize ethylene on the solid catalyst component when an ethylene polymer is produced using the above catalyst system. For example, Patent Document 9 discloses a catalyst system comprising a transition metal compound of Groups 4 to 6 of the periodic table, a compound that can react with the transition metal compound or a derivative thereof to form an ionic complex, and an organoaluminum compound. A method is described in which prepolymerization of olefin is performed and main polymerization mainly comprising olefin is performed using the obtained granular prepolymerization catalyst. Patent Document 10 describes an olefin polymerization catalyst obtained by prepolymerizing an olefin with a catalyst component comprising a particulate carrier, a transition metal compound of Groups 8 to 10 of the periodic table, and an organometallic compound. .
These methods were expected to improve polymer powder properties and polymerization activity by performing prepolymerization. However, in actual polymerization reaction, particle crushing and fine powder generation were also expected. It was seen and it was not enough in terms of activity.

  On the other hand, all of the catalyst systems proposed in these prior arts require a catalyst preparation step and / or a catalyst washing step before using the catalyst, and a large amount of washing solvent is required. Further, a large amount of waste liquid after washing is generated in this washing step. These have given big restrictions to catalyst preparation, and reduction of the washing | cleaning process was desired. In a conventional catalyst, if this washing step is omitted or the washing operation is not sufficient, powder properties deteriorate due to the formation of an amorphous polymer in the reactor when the catalyst is used for polymerization. It was a cause of the phenomenon of polymer adhesion inside. Patent Documents 11 and 12 disclose a technique that can polymerize a polymer having high activity and excellent powder properties without causing adhesion to a reactor. Although these were very excellent techniques, at least a catalyst washing step was required in the catalyst preparation step.

Japanese Examined Patent Publication No. 04-012283 DE31271332 Taube, et al. , J .; Organomet. Chem. , 347, C9 (1988) Jordan, et al. , J .; Am. Chem. SoE-109, 4111 (1987) Japanese Translation of National Publication No. 01-501950 Japanese translation of PCT publication No. 01-502036 Japanese Patent Laid-Open No. 05-301917 Japanese Patent Laid-Open No. 06-136047 JP 09-059310 A JP 11-269222 A JP 09-194520 A JP 09-272713 A WO03 / 035704 Publication JP 2004-027200 A

  Therefore, it is desired to develop a catalyst that can polymerize a polymer having high activity and excellent powder properties without causing adhesion to the reactor, etc., and further omitting the catalyst preparation step and the washing step before using the catalyst. The present invention provides such a novel olefin polymerization catalyst and an olefin polymerization method using the same.

In view of such a current situation, the present inventors have achieved a highly active, effective and efficient polymer powder that does not cause a phenomenon such as adhesion to a reactor during polymerization and that is extremely excellent in powder properties. The present invention has been accomplished by intensively studying to find a method for obtaining a novel catalyst system that can be manufactured in a simple manner and that can further eliminate the catalyst preparation step and the washing step before using the catalyst. That is, the present invention
1) A catalyst for olefin polymerization composed of a solid component [A] and a liquid component [B], wherein the solid component [A] contains a Lewis acidic compound in a range of 0.01 mmol / g to 0.4 mmol / g. An adsorbable carrier [C], a transition metal compound component [D] belonging to the group consisting of Groups 3 to 11 of the periodic table and soluble in a hydrocarbon solvent, and a transition metal compound component [D ], And the precursor of the carrier [C] is a group 2 or 3 in the periodic table , which is capable of forming a metal complex having catalytic activity . An inorganic solid oxide of an element belonging to the group consisting of Group 4, Group 13 and Group 14, having an average particle size of 1 to 20 microns; E. T.A. The specific surface area is 300 m ² / g or more and 600 m ² / g or less, and the transition metal compound [D] includes a transition metal compound (D-1) represented by the following formula (8):
(Wherein M ⁶ is a transition gold selected from the group consisting of titanium, zirconium and hafnium.
A transition metal having a formal oxidation number of +2, +3 or +4, and each R ¹² independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, Represents a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of a cyano group, a halogen atom and a composite group thereof, provided that the substituent R ¹² is a carbon atom having 1 to 8 carbon atoms. When it is a hydrogen group, a silyl group, or a germyl group, in some cases, two adjacent substituents R ¹² are bonded to each other to form a divalent group, and thereby bonded to the two adjacent substituents R ¹² , respectively. To form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring , and each X ⁵ independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 1 or more. 18 or less hydrocarbyloxy groups, charcoal Hydrocarbylamino group having 1 to 18 carbon atoms, silyl group, hydrocarbylamide group having 1 to 18 carbon atoms, hydrocarbyl phosphide group having 1 to 18 carbon atoms, hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite thereof A substituent having 1 or more and 20 or less non-hydrogen atoms selected from the group consisting of a group, provided that in some cases, the two substituents X ⁵ work together to neutralize 4 to 30 carbon atoms Forming a conjugated diene or divalent group,
Y ³ represents —O—, —S—, —NR ¹³ — or —PR ¹³ — , wherein R ¹³ represents a hydrogen atom.
A hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms. Or a combination of these,
Z ² represents Si (R ¹³ ) ₂ , C (R ¹³ ) ₂ , Si (R ¹³ ) ₂ —Si (R ¹³ ) ₂ , C (R ¹³ ) —
C (R ¹³ ) ₂ , C (R ¹³ ) = C (R ¹³ ), C (R ¹³ ) ₂ —Si (R ¹³ ) ₂ , Si (R ¹³ ) ₂ —C (R ¹³ ) ₂ or Ge (R ¹³ ) represents ₂ and x is 1, 2 or 3),
The liquid component [B] is composed of an organomagnesium compound [G] soluble in a hydrocarbon solvent represented by the following formula (1) and a compound [J] selected from amines, alcohols, and siloxane compounds. A catalyst for olefin polymerization.
(M ¹ ) _a (Mg) _b (R ¹ ) _c (R ² ) _d (1)
[Wherein M ¹ is a metal atom belonging to the group consisting of groups 1 to 3 and groups 11 to 13 of the periodic table, and R ¹ and R ² are hydrocarbons having 2 to 20 carbon atoms. A, b, c, d are real numbers satisfying the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ¹ )]

2) The olefin polymerization catalyst as described in 1) above, wherein the activating agent [E] contains at least an activating compound (E-1) represented by the following formula (3).
[AH] ^{k +} [M ^Three _m (Q ¹ ) _n ] ^k-       (3)
(Where [AH] ^{k +} Represents a proton-donating Bronsted acid, wherein A represents a neutral Lewis base, k is an integer of 1 to 7, and [M ^Three _m (Q ¹ ) _n ] ^k- Represents a compatible non-coordinating anion, provided that M ^Three Represents a metal or metalloid belonging to the group consisting of groups 5 to 15 of the periodic table, Q ¹ Each independently represents a hydride, a halide, a dihydrocarbylamide group having 2 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, and 1 or more carbon atoms. Selected from the group consisting of up to 40 substituted hydrocarbon groups, provided that Q is a halide. ¹ Is 1 or less, m is an integer of 1 or more and 7 or less, n is an integer of 2 or more and 14 or less, k is as defined above, and nm = k. )

3) The transition metal compound component [D] is an organomagnesium compound (D-1) soluble in the transition metal compound (D-1) represented by the above formula (8) and the hydrocarbon solvent represented by the following formula (4) The catalyst for olefin polymerization according to 1) or 2) above, which is a mixture with -2).
(M ^Four ) _p (Mg) _q (R ^Three ) _r (R ^Four ) _s (OR ^Five ) _t       (4)
[Where M ^Four Is a metal atom belonging to the group consisting of Groups 1 to 3 and Groups 11 to 13 of the Periodic Table,
R ^Three , R ^Four And R ^Five Is a hydrocarbon group having 2 to 20 carbon atoms,
p, q, r, s, and t are numbers satisfying the following relationship.
0 ≦ p, 0 <q, 0 ≦ r, 0 ≦ s, 0 ≦ t, r + s> 0, 0 ≦ t / (r + s) ≦ 2, p × u + 2q = r + s + t (where u is M ^Four Valence))]

4) The activator [E] is a mixture of the activated compound (E-1) represented by the above formula (4) and the organoaluminum compound (E-2). ) To olefin polymerization catalyst according to any one of 3) above.
5) The liquid component [B] is composed of an organomagnesium compound [G] soluble in a hydrocarbon solvent represented by the following formula (1) and a compound [J] selected from amines, alcohols, and siloxane compounds. The catalyst for olefin polymerization according to any one of 1) to 4) above, wherein
(M ¹ ) _a (Mg) _b (R ¹ ) _c (R ² ) _d         (1)
[Where M ¹ Is a metal atom belonging to the group consisting of lithium, sodium, potassium, beryllium, zinc, boron, aluminum, R ¹ And R ² Is a hydrocarbon group having 2 to 20 carbon atoms, and a, b, c and d are real numbers satisfying the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is M ¹ Valence))]
6) A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of 1) to 5) above.

  According to the present invention, a polymer having high activity and excellent powder properties can be polymerized without causing adhesion to the reactor, and further, the catalyst preparation step and the washing step before using the catalyst can be omitted. An olefin polymerization catalyst and an olefin polymerization method using the same can be provided.

Hereinafter, the present invention will be specifically described.
In the present invention, the solid component [A] includes a carrier [C] capable of adsorbing a Lewis acidic compound in a range of 0.01 mmol / g to 0.4 mmol / g, and groups 3 to 1 of the periodic table. A transition metal compound component [D] belonging to the group consisting of group 11 and soluble in a hydrocarbon solvent and an activity capable of reacting with the transition metal compound component [D] to form a metal complex having catalytic activity It consists of the agent [E].
First, the carrier [C] capable of adsorbing a Lewis acidic compound will be described.
In the present invention, the carrier [C] capable of adsorbing the Lewis acidic compound means that the Lewis acidic compound is supported by physical adsorption or chemical adsorption [C] when the carrier [C] is treated with the Lewis acidic compound. A carrier that is adsorbed on the surface.
The Lewis acidic compound in the present invention is an organometallic compound containing a metal element belonging to the group consisting of Groups 2 to 13 of the periodic table, and more preferably organoaluminum or organomagnesium.

Among the preferable organoaluminum compounds, a compound represented by the following formula (5) is more preferable.
Al (R ⁶ ) _v (X ² ) _(3-v) (5)
(In the formula, each R ⁶ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ² is each independently A halide, a hydride, or an alkoxide group having 1 to 10 carbon atoms, and v is a real number having 1 to 3 carbon atoms).
Examples of the group R ⁶ in the formula (5) include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group and tolyl group. Examples of the group X ² in the formula (5) include a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, and a chlorine atom.

Specific examples of the organoaluminum compound represented by the above formula (5) include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and their trialkyls. The reaction product of an aluminum compound and alcohol (for example, methanol, ethanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol), etc. are mentioned. Examples of this reaction product include methoxydimethylaluminum, ethoxydiethylaluminum, butoxydibutylaluminum and the like. In the case of producing such a reaction product, the molar ratio of trialkylaluminum to alcohol is preferably in the range of 0.3 to 20, more preferably in the range of 0.5 to 5, More preferably, it is in the range of not less than 8 and not more than 3. These organoaluminum compounds may be used alone or in combination of two or more kinds of organoaluminum compounds.
In addition, an organoaluminum oxy compound described later as an example of the activator [E] can also be used as the Lewis acidic compound.

Among the above preferred organomagnesium compounds, compounds represented by the following formula (6) are more preferred.
Mg (R ⁷ ) _w (X ³ ) _(2-w) (6)
(In the formula, each R ⁷ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ³ each independently. A halide, a hydride, or an alkoxy group having 1 to 10 carbon atoms, and w is a real number having 1 to 2 carbon atoms).
Examples of the group R ^{7 in} the above formula (6) include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and the like. Examples of X ³ in the formula (6) include a methoxy group, an ethoxy group, a butoxy group, a hydroxy group, and a chloro group.
Specific examples of the organomagnesium compound represented by the above formula (6) include diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium and the like. These organomagnesium compounds may be used alone or in combination of two or more kinds of organomagnesium compounds.
The organoaluminum compounds and organomagnesium compounds represented by the above formulas (5) and (6) may be used as a mixture.

The carrier [C] capable of adsorbing a Lewis acidic compound used in the present invention can be produced from a solid material (hereinafter referred to as a precursor of the carrier [C]) by the method described below.
1) The saturated adsorption amount of the Lewis acidic compound adsorbed to the precursor of the carrier [C] is quantified in advance, and an amount of Lewis acidic compound smaller than the saturated adsorption amount is adsorbed to the precursor of the carrier [C].
2) First, the precursor of the carrier [C] is heat-treated to remove the water (crystal water, adsorbed water, etc.) present on the surface, and then the same operation as in 1) is performed, so that the saturated adsorption amount is exceeded. A small amount of Lewis acidic compound is adsorbed.
In the present invention, the saturated adsorption amount of the Lewis acidic compound is the amount of surface hydroxyl group (mmol) of the precursor of the carrier [C] at 20 ° C. with stirring in a 50 g / l hexane slurry of the precursor of the carrier [C]. / G), a Lewis acidic compound having a molar number 1.4 times the total molar amount of surface hydroxyl groups contained in the whole slurry calculated from the above is added and reacted for 2 hours. It is the amount of adsorption calculated from the molar reduction amount of the Lewis acidic compound. In the present invention, the molar amount of the surface hydroxyl group of the carrier [C] precursor is determined by reacting ethoxydiethylaluminum with the surface hydroxyl group of the carrier [C] precursor to generate ethane gas, and quantifying the amount of ethane gas generated. It was calculated by doing.

  In the present invention, the carrier [C] precursor removes water (crystal water, adsorbed water, etc.) present on the surface of the carrier [C] precursor by heat treatment before adsorbing the Lewis acidic compound. It is preferable to keep it. There is no particular limitation on the heat treatment of the precursor of the carrier [C], but for example, a temperature of 150 ° C. or higher and 1,000 ° C. or lower, preferably 250 ° C. or higher and 800 ° C. or lower in an inert atmosphere or a non-reducing atmosphere. Therefore, it can be performed by a treatment of 1 hour to 50 hours. In the present invention, the non-reducing atmosphere is an oxygen atmosphere or an air atmosphere that does not substantially contain moisture, and is sufficiently dried by circulating in a desiccant such as molecular sieves. An atmosphere is preferred. In this non-reducing atmosphere, an inert gas such as nitrogen or argon may coexist. In addition, when the saturated adsorption amount of the Lewis acidic compound as the precursor of the carrier [C] is 0.01 mmol / g or more and 0.4 mmol / g or less by this heat treatment, a step of adsorbing the Lewis acidic compound is performed. It is possible to omit and use the precursor of the carrier [C] as the carrier [C].

  Examples of the precursor of the carrier [C] include porous polymer materials (provided that the matrix is, for example, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethylene / vinyl ester copolymer, styrene / divinylbenzene copolymer) Thermosetting properties such as coalescence, part of ethylene / vinyl ester copolymer or completely saponified polyolefin and its modified products, thermoplastic resin such as polyamide, polycarbonate, polyester, phenol resin, epoxy resin, urea resin, melamine resin Inorganic solid oxides of elements belonging to the group consisting of Group 2, Group 3, Group 4, Group 13, Group 14 of Periodic Table (for example, silica, alumina, magnesia, magnesium chloride) , Zirconia, titania, boron oxide, calcium oxide, zinc oxide, oxidation Potassium, vanadium pentoxide, chromium oxide, thorium oxide, or mixtures or complex oxides thereof thereof), and the like. Examples of composite oxides containing silica include composites of silica and oxides of elements selected from elements belonging to groups 2 and 13 of the periodic table, such as silica-magnesia and silica-alumina. An oxide is mentioned. In the present invention, the precursor of the support [C] is a composite oxide of silica, alumina, and silica and an oxide of an element selected from the group consisting of Groups 2 and 13 of the periodic table. It is preferable to be selected. Of these inorganic solid oxides, silica is particularly preferred.

In the present invention, the shape of the silica product used as the precursor of the carrier [C] is not particularly limited, and the silica may have any shape such as a granular shape, a spherical shape, an agglomerated shape, and a fume shape. Preferred examples of commercially available silica products include SD3216.30, SP-9-10046, Devison Cyroid ™ (Syloid ™) 245, Devison 948 or Devison 952 [all above, Grace Devison (WR Devison ( Aerosil 812 [Degusa AG (Germany)], ES70X [Crossfield (USA)], P-6, P-10, Q-6 or Q10 [Fuji Silysia (Japan) Country)], and the like. Among these, Q-6 is particularly preferable.
The average particle size of the precursor of the carrier [C] used in the present invention is not particularly limited, but the average particle size measured with a laser particle size distribution analyzer is preferably 5 μm or more and 20 μm or less. If this average particle size is less than 5 μm, it is not preferred because it may interfere with stable olefin polymerization by adhering in the polymerization vessel or in the piping, and if it is greater than 20 μm, the polymerization activity of the catalyst may be reduced. Therefore, it is not preferable.

B. A precursor of the carrier [C] used in the present invention, E. T. T. The specific surface area determined by the nitrogen gas adsorption method by (Brunauer-Emmett-Teller) is not particularly limited, but is preferably 10 m ² / g or more and 1,000 m ² / g or less, more preferably 100 m ² / g or more. It is 600 m ² / g or less, and more preferably 300 m ² / g or more and 600 m ² / g or less. If the specific surface area is less than 10 m ² / g, the catalyst activity may be low, which is not preferable. If the specific surface area is more than 1000 m ² / g, the strength of the support [C] may be decreased, which is not preferable. One representative example of the precursor of the carrier [C] having such a high specific surface area is a porous material having many pores.
In the present invention, the pore volume of the precursor of the carrier [C] obtained by the nitrogen gas adsorption method is not particularly limited, but is preferably 0.1 cm ³ / g or more and 5 cm ³ / g or less, more preferably 0.8. 1 cm ³ / g or more and 3 cm ³ / g or less, more preferably 0.2 cm ³ / g or more and 2 cm ³ / g or less. If it is less than 0.1 cm ³ / g, the catalytic activity may be low, which is not preferable. If it is more than 5 cm ³ / g, the strength of the support [C] may decrease, which is not preferable.

In the present invention, the adsorption amount of the Lewis acidic compound on the carrier [C] is 0.01 mmol / g or more and 0.4 mmol / g or less, preferably 0.02 mmol / g or more and 0.35 mmol / g or less, More preferably, it is 0.03 mmol / g or more and 0.3 mmol / g or less. When the amount of the Lewis acidic compound adsorbed is less than 0.01 mmol / g, the transition metal compound component [D] and the activator [E] are eluted from the catalyst. Since it may be necessary, it is not preferable, and when it is larger than 0.4 mmol / g, the catalyst activity may be decreased, which is not preferable.
In the present invention, the saturated adsorption amount of the Lewis acidic compound with respect to the precursor of the carrier [C] is not particularly limited, but is preferably 0.01 mmol / g or more and 5 mmol / g or less, 0.01 mmol / g It is preferably 3 mmol / g or less. When the amount is less than 0.01 mmol / g, the transition metal compound component [D] and the activator [E] are eluted, which may cause a catalyst preparation step or a catalyst washing step before using the catalyst. If it is greater than 3 mmol / g, the catalytic activity may decrease, which is not preferable. The saturated adsorption amount of the Lewis acidic compound with respect to the carrier [C] precursor can be controlled by the heat treatment conditions of the carrier [C] precursor.

Next, the transition metal compound component [D] soluble in the hydrocarbon solvent used in the present invention will be described.
In the present invention, the transition metal compound component [D] is not particularly limited, but at least a transition metal compound belonging to the group consisting of Group 3 to Group 11 of the periodic table represented by the following formula (2) ( D-1) is preferably included.
(L ¹ ) _f (Z ¹ ) _h (M ² ) (X ¹ ) _i (Y ¹ ) _j (2)
[Wherein L ¹ is independently selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. Represents a binding cyclic anion ligand, and the ligand optionally has 1 or more and 8 or less substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, A halogen atom, a halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, Hydrocarbylphosphino group having 1 to 12 carbon atoms, silyl group, aminosilyl group, hydrocarbyloxysilyl group having 1 to 12 carbon atoms And a substituent having up to 20 non-hydrogen atoms selected from the group consisting of halosilyl groups,
M ² is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and is a transition having a η ⁵ bond to at least one ligand L ¹ Representing metal,
Z ¹ is a divalent substituent having up to 50 non-hydrogen atoms, and binds to each of L ¹ and M ² with a single valence, thereby cooperating with L ¹ and M ^2. Represents a divalent substituent that forms a metallocycle,
X ¹ is each independently a monovalent anionic σ-bonded ligand, a divalent anionic σ-bonded ligand that binds to M ^{2 in} a divalent manner, and L ¹ and M ² each. Represents an anionic σ-bonded ligand having 1 or more and 60 or less non-hydrogen atoms selected from the group consisting of divalent anionic σ-bonded ligands that bind with each valence of 1;
Y ¹ each independently represents a neutral Lewis base coordination compound having 1 to 40 non-hydrogen atoms,
f is 1 or 2, provided that when f is 2, in some cases two ligands L ¹ are bonded to each other via a divalent group having 1 to 20 non-hydrogen atoms. And the divalent group includes a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and 1 or more carbon atoms. A group selected from the group consisting of 12 or less hydrocarbyleneamino groups, silanediyl groups, halosilanediyl groups, and silyleneamino groups;
h is 0 or 1,
i is 0, 1 or 2, provided that X ¹ is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to L ¹ and M ² I is an integer that is one or more smaller than the formal oxidation number of M ² , and when X ¹ is a divalent anionic σ-bonded ligand bonded only to M ² , i is M ^An integer that is (f + 1) or more smaller than the formal oxidation number of ² ,
j is 0, 1 or 2; ]

Examples of the ligand X ¹ in the compound of the above formula (2) include a halide, a hydrocarbon group having 1 to 60 carbon atoms, a hydrocarbyloxy group having 1 to 60 carbon atoms, and 1 to 60 carbon atoms. A hydrocarbyl amide group having 1 to 60 carbon atoms, a hydrocarbyl sulfide group having 1 to 60 carbon atoms, a silyl group, and a composite group thereof.
Examples of the neutral Lewis base coordination compound Y ^{1 in} the compound of the above formula (2) include phosphine, ether, amine, olefin having 2 to 40 carbon atoms, diene having 1 to 40 carbon atoms, these And a divalent group derived from the above compound.

Examples of the component (D-1) used in the present invention include compounds represented by the following formula (7).
(Wherein R ⁸ and R ¹¹ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic group having a hydrocarbon group on the ring having 7 to 20 carbon atoms in total, R ⁹ and R ¹⁰ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ⁹ and R ¹⁰ may be bonded to each other to form a ring, and X ⁴ and Y ² are Each independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M ⁵ represents nickel or palladium.)

In the above formula (7), the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R ⁸ and R ¹¹ is a linear or branched alkyl group having 1 to 20 carbon atoms or 3 or more carbon atoms. 20 or less cycloalkyl groups, specifically, methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl Group, 2-methylpentyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethyl-4-methylpentyl group, 2-propylheptyl group, 2-ethyl-5-methyloctyl group, Octyl, nonyl, decyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. It is. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group.
Examples of the aromatic group having a hydrocarbon group on a ring having 7 to 20 carbon atoms are linear or branched having 1 to 10 carbon atoms on an aromatic ring such as a phenyl group or a naphthyl group. And a group into which one or more alkyl or cyclic alkyl groups are introduced. As R ⁸ and R ¹¹ , an aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropylphenyl group is particularly preferable.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ include, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like. Here, as the linear or branched alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 20 carbon atoms, the aliphatic group having 1 to 20 carbon atoms in R ⁸ and R ¹¹ is used. The same thing as what was illustrated in description of a hydrocarbon group can be mentioned. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, tolyl group, xylyl group, naphthyl group, and methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and Examples thereof include a phenethyl group.
R ⁹ and R ¹⁰ may be bonded to each other to form a ring. On the other hand, examples of the halogen atom in X ⁴ and Y ² include a chlorine, bromine or iodine atom, and the hydrocarbon group having 1 to 20 carbon atoms is the carbon number in R ⁹ and R ¹⁰ described above. The hydrocarbon group having 20 or less is as described above. X ⁴ and Y ² are particularly preferably a bromine atom or a methyl group. X ⁴ and Y ² may be the same or different.

In the present invention, the transition metal compound (D-1) is preferably a transition metal compound represented by the above formula (2) (where f = 1). Preferable examples of the compound represented by the formula (2) (where f = 1) include a compound represented by the following formula (8).

(In the formula, M ⁶ represents a transition metal selected from the group consisting of titanium, zirconium and hafnium, and represents a transition metal having a formal oxidation number of +2, +3 or +4, and R ¹² each independently represents: Substitution having 1 to 20 non-hydrogen atoms selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom and a composite group thereof Wherein the substituent R ¹² is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group, and in some cases, two adjacent substituents R ¹² are bonded to each other to form a divalent group. Thereby forming a ring in cooperation with a bond between two carbon atoms of the cyclopentadienyl ring bonded to each of the two adjacent substituents R ¹² , wherein X ⁵ is independently Halide, carbon A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, a hydrocarbylamide group having 1 to 18 carbon atoms, and one or more carbon atoms Represents a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of 18 or less hydrocarbyl phosphide groups, hydrocarbyl sulfide groups having 1 to 18 carbon atoms and complex groups thereof, In some cases, the two substituents X ⁵ cooperate to form a neutral conjugated diene or divalent group having 4 to 30 carbon atoms,
Y ³ represents —O—, —S—, —NR ¹³ — or —PR ¹³ —, wherein R ¹³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 to 8 carbon atoms. A hydrocarbyloxy group, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof.
Z ² is Si (R ¹³ ) ₂ , C (R ¹³ ) ₂ , Si (R ¹³ ) ₂ -Si (R ¹¹ ) ₂ , C (R ¹³ ) -C (R ¹³ ) ₂ , C (R ¹³ ) = C (R ¹³ ), C (R ¹³ ) ₂ —Si (R ¹³ ) ₂ , Si (R ¹³ ) ₂ —C (R ¹³ ) ₂ or Ge (R ¹³ ) ₂ is represented, and x is 1, 2 or 3 Is).

Specific examples of the transition metal compound (D-1) used in the present invention include the following compounds.
Bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis (cyclopentadienyl) phenylzirconium hydride, bis (cyclopentadienyl) benzylzirconium hydride, bis (cyclopentadienyl) ) Neopentylzirconium hydride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (cyclopentadienyl) ) Zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis ( Clopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dihydride, bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) Zirconium diethyl, ethylenebis (indenyl) zirconium dihydride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4-methyl-1-indenyl) zirconium dimethyl, ethylenebis (5 -Methyl-1-indenyl) zirconium dimethyl, ethylenebis (6-methyl-1-indenyl) zirconium dimethyl, ethylenebis (7-methyl-1-indenyl) zyl Nitrodimethyl, ethylenebis (5-methoxy-1-indenyl) zirconium dimethyl, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) dimethylzirconium, ethylene Bis- (4,7-dimethoxy-1-indenyl) zirconium dimethyl, methylene bis (cyclopentadienyl) zirconium dihydride, methylene bis (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) zirconium dihydride, isopropyl Liden (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dihydride, isopropylidene (cyclopentadienyl) Ru-fluorenyl) zirconium dimethyl, silylene bis (cyclopentadienyl) zirconium dihydride, silylene bis (cyclopentadienyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) zirconium dihydride, dimethylsilylene (cyclopentadienyl) zirconium dimethyl , [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butyramide) (tetramethyl-η ⁵ -cyclopentadienyl) ) dimethylsilane] titanium dimethyl, [(N-methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) dimethyl silane] titanium dimethyl, [(N-phenyl-amide) (tetramethyl-eta ⁵ - cyclopentyl Tajieniru) dimethylsilane] titanium dimethyl, [(N-benzylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) dimethyl silane] titanium dimethyl, [(N-t-butylamido) (eta ⁵ - cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butylamide) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamide) (η ⁵ -cyclopentadienyl) -1 , 2-ethanediyl] titanium dimethyl, [(N-methylamido) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamido) (η ⁵ -indenyl) dimethylsilane] titanium dimethyl, (N- benzylamide) (eta ⁵ - indenyl) dimethylsilane] Data chloride-dimethyl.

Specific examples of the transition metal compound (D-1) used in the present invention include “dimethyl” in the names of the zirconium and titanium compounds listed above as specific examples of the transition metal compound (D-1). (This appears immediately after the last part of the name of each compound, that is, the part of “zirconium” or “titanium”, and corresponds to the part of X ⁵ in the formula (8). ) May be replaced with any of the compounds listed below.
“Dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4-diyl”, “s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene” "S-trans-η ⁴ -3-methyl-1,3-pentadiene", "s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene", "s-trans-η ⁴ -2" , 4-hexadiene, "" s- trans eta ⁴ -1,3-pentadiene "," s- trans eta ^{4-1,4-ditolyl-1,3-butadiene,} "" s- trans eta ⁴ - 1,4-bis (trimethylsilyl) -1,3-butadiene ”,“ s-cis-η ⁴ -1,4-diphenyl-1,3-butadiene ”,“ s-cis-η ⁴ -3-methyl-1 ” , 3-pentadiene "," s- cis -η ⁴ -1,4- dibenzyl-1,3-Breakfast Diene "," s- cis -η ⁴ -2,4- hexadiene "," s- cis -η ⁴ -1,3- pentadiene "," s- cis -η ⁴ -1,4- ditolyl-1,3 -Butadiene "," s-cis-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene ", and the like.

The transition metal compound (D-1) used in the present invention can be synthesized by a generally known method. As an example of a preferable synthesis method of the transition metal compound used as the transition metal compound (D-1), the method disclosed in US Pat. No. 5,491,246 can be exemplified.
In the present invention, these transition metal compounds (D-1) may be used alone or in admixture of two or more.
In the present invention, the transition metal compound (D-1) is preferably used by mixing with an organomagnesium compound (D-2) soluble in a hydrocarbon solvent.
The organomagnesium compound (D-2) used in the present invention is represented by the following formula (4).
(M ⁴ ) _p (Mg) _q (R ³ ) _r (R ⁴ ) _s (OR ⁵ ) _t (4)
[Wherein M ⁴ is a metal atom belonging to the group consisting of groups 1 to 3 of the periodic table,
R ³ , R ⁴ and R ⁵ are hydrocarbon groups having 2 to 20 carbon atoms,
p, q, r, s, and t are numbers satisfying the following relationship.
0 ≦ p, 0 <q, 0 ≦ r, 0 ≦ s, 0 ≦ t, r + s> 0, 0 ≦ t / (r + s) ≦ 2, p × u + 2q = r + s + t (where u is the valence of M ⁴ ) ]

The organomagnesium compound (D-2) used in the present invention is shown as a form of a complex compound of organomagnesium that is soluble in a hydrocarbon solvent, but it is a complex of R ³ Mg and other metal compounds. Includes everything. The relational expression p × u + 2q = r + s + t of the symbols p, q, r, s, and t represents the stoichiometry between the valence of the metal atom and the substituent.
In the above formula, the hydrocarbon group represented by R ³ or R ⁴ is an alkyl group, a cycloalkyl group or an aryl group, and examples thereof include an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, and a 1-methyl group. Propyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, 2-methylpentyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethyl-4-methylpentyl group, 2 -Propyl heptyl group, 2-ethyl-5-methyloctyl group, octyl group, nonyl group, decyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, etc. Can be mentioned. An alkyl group is preferable, and a primary alkyl group is particularly preferable.
In the case of p> 0, as the metal atom M ⁴ , a metal element belonging to the group consisting of Groups 1 to 3 and Groups 11 to 13 of the periodic table can be used. For example, lithium, sodium, potassium, Examples include beryllium, zinc, boron, and aluminum, with aluminum, boron, beryllium, and zinc being particularly preferable. In the present invention, the molar ratio q / p of magnesium to the metal atom M4 is not particularly limited, but is preferably in the range of 0.1 to 30 and 0.5
The range of 10 or less is more preferable.

In the present invention, when p = 0 in the above formula (4), an organomagnesium compound that is soluble in a hydrocarbon solvent is preferred, and R ³ and R ⁴ represent the following three groups (1), ( More preferably, it belongs to any one of 2) and (3).
(1) At least one of R ³ and R ⁴ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ³ and R ⁴ have 4 to 6 carbon atoms. Yes, and at least one is a secondary or tertiary alkyl group.
(2) R ³ and R ⁴ are alkyl groups having different carbon atoms, preferably R ¹ is an alkyl group having 2 or 3 carbon atoms, and R ³ has 4 to 20 carbon atoms. An alkyl group of
(3) At least one of R ³ and R ⁴ is a hydrocarbon group having 6 to 20 carbon atoms, preferably R ³ and R ⁴ are both alkyl groups having 6 to 20 carbon atoms.

Next, R ³ and R ⁴ are specifically shown. As the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (1), 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 2-methylbutyl group, 2 -Ethylpropyl group, 2,2-dimethylpropyl group, 2-methylpentyl group, 2-ethylbutyl group, 2,2-dimethylbutyl group, 2-methyl-2-ethylpropyl group, etc. are used, and 2-methyl A pentyl group is particularly preferred. In (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group and a propyl group, and an ethyl group is particularly preferable. Examples of the alkyl group having 4 to 20 carbon atoms include a butyl group, an amyl group, a hexyl group, an octyl group, and the like, and a butyl group and a hexyl group are particularly preferable. Examples of the alkyl group having 6 to 20 carbon atoms in (3) include a hexyl group, an octyl group, a decyl group, and a phenyl group. An alkyl group is preferable, and a hexyl group is particularly preferable.
In general, increasing the number of carbon atoms in the alkyl group makes it easier to dissolve in a hydrocarbon solvent, but the viscosity of the solution tends to increase, and use of an alkyl group having a longer chain than necessary is not preferable in handling. In addition, although the said organomagnesium compound is used as a hydrocarbon solution, even if trace amount of complexing agents, such as ether, ester, and amine, are contained in the solution slightly or can remain, it can be used.

Next, the alkoxy group (OR ⁵ ) of the above formula (4) will be described. The hydrocarbon group represented by R ^5, preferably an alkyl group or aryl group having 3 to 10 carbon atoms.
Specifically, for example, propyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, 2-methylpentyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethyl-4-methylpentyl group, 2-propylheptyl group, 2-ethyl-5-methyloctyl group, n-octyl group, n-decyl group, phenyl group group A butyl group, 1-methylpropyl, 2-methylpentyl group and 2-ethylhexyl group are preferable.

These organomagnesium compounds or organomagnesium complexes include an organomagnesium compound represented by the following formula (9) or formula (10) and an organometallic compound represented by the following formula (11) or formula (12). , Hexane, heptane, cyclohexane, benzene, toluene, etc., in an inert hydrocarbon medium, reacted in the range of 10 ° C. to 150 ° C., and if necessary, an alcohol having a hydrocarbon group represented by R ⁵ Alternatively, it can be synthesized by a method of reacting with a hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ⁵ and / or a hydrocarbyloxyaluminum compound that is soluble in a hydrocarbon solvent.
R ³ MgX ⁶ , (9)
(R ³ is as defined in formula (4) above, and X ⁶ is halogen.)
(R ³ ) ₂ Mg (10)
(R ³ is as defined in the above formula (4).)
M ⁴ (R ⁴ ) _u (11)
(M ⁴ , R ⁴ and u are as defined in the above formula (4).)
M ⁴ (R ⁴ ) _(u-1) H (12)
(M ⁴ , R ⁴ and u are as defined in the above formula (4).)

In the present invention, when an organic magnesium component soluble in a hydrocarbon is reacted with an alcohol, the order of the reaction is not particularly limited, a method of adding alcohol to the organic magnesium component, an organic magnesium component in the alcohol, Any of the method of adding, or the method of adding both simultaneously is preferable. In the present invention, the reaction ratio between the organic magnesium component soluble in hydrocarbon and the alcohol is not particularly limited. The range of t / (p + q) is preferably 0 ≦ t / (p + q) ≦ 2, and more preferably 0 ≦ t / (p + q) <1.
In the present invention, the method of mixing (D-1) and (D-2) is not particularly limited. The method of adding (D-2) to (D-1) or the component (D-2) (D-1) or a method of adding both at the same time, and any of these methods are preferred.

In the present invention, the molar ratio of (D-2) / (D-1) is not particularly limited, but the molar ratio of (D-2) / (D-1) is 0.005 or more and 5 or less. Preferably, it is 0.01 or more and 2 or less. When the molar ratio of (D-2) / (D-1) is less than 0.005, (D-2) is insufficient and the activity may be lowered. Since (D-2) is excessive and the transition metal compound component [D] and the activator [E] are eluted, there is a possibility that a catalyst washing step may be required before the catalyst preparation step or the catalyst use. .
In the present invention, the transition metal compound (D-1) the carrier [C] is preferably used in an amount of 5 × 10 ^-6 mol to 10 ^-2 mol or less with respect to 1 g, 10 ^-5 mol to 10 ^- More preferably, it is used in an amount of ³ mol or less. [A] When (D-1) per 1 g is less than 5 × 10 ⁻⁶ mol, the activity per 1 g of the catalyst is undesirably lowered, and when it is larger than 10 ⁻² mol, (D Since -1) is eluted, a catalyst washing step may be required before the catalyst preparation step or the catalyst use, which is not preferable.

Next, the activator [E] will be described.
In the present invention, the activator [E] is not particularly limited, but is an activated compound (E) that can react with at least the transition metal compound component [D] to form a metal complex having catalytic activity. -1) is preferably included.
In the present invention, for example, an organoaluminum oxy compound is used as the activating compound (E-1). The preferred organoaluminum oxy compound used in the present invention can be produced, for example, by the following method and is usually obtained as a solution in a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
The organoaluminum oxy compound may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered solution of the organoaluminum oxy compound by distillation, it may be redissolved in a solvent or suspended in a poor solvent of the organoaluminum oxy compound.

Specific examples of the organoaluminum compound used in preparing the organoaluminum oxy compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tri (1-methylethyl) aluminum, tributylaluminum, and tri (1-methylpropyl) aluminum. , Tri (2-methylpropyl) aluminum, tri (1,1-dimethylethyl) aluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., trialkylaluminum, tricyclohexylaluminum, tricyclooctylaluminum Such as tricycloalkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum chloride Dialkylaluminum halides such as imide, diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride, di (2-methylpropyl) aluminum hydride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide, diethylaluminum phenoxide, etc. Examples include dialkylaluminum aryloxide.
Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

In the present invention, clay, clay mineral or ion-exchange layered compound can also be preferably used as the activating compound (E-1). In this case, an organoaluminum compound represented by the following formula (5) is preferably used at the same time, and trialkylaluminum is more preferable.
Al (R ⁶ ) _v (X ² ) _(3-v) (5)
(In the formula, each R ⁶ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ² is each independently A halide, a hydride, or an alkoxide group having 1 to 10 carbon atoms, and v is a real number having 1 to 3 carbon atoms).
The clay used in the present invention is usually preferably composed mainly of a clay mineral, and the ion-exchangeable layered compound has a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force. A compound that can be exchanged is preferable. Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl ₂ type, and a CdI ₂ type. These clays, clay minerals, and ion-exchange layered compounds are not limited to natural ones, and artificial synthetic products can also be used.

Specific examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, Naclite, dickite, halloysite, etc. are mentioned, and examples of the ion exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H. ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti Examples thereof include crystalline acidic salts of polyvalent metals such as (HPO ₄ ) ₂ and γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.
Such clays, clay minerals, and ion-exchangeable layered compounds have a pore volume of 2 nm or more in radius measured by mercury porosimetry from 0.1 cm ³ / g to 10 cm ³ / g from the viewpoint of polymerization activity. Those having a concentration of 0.3 cm ³ / g or more and 5 cm ³ / g or less are particularly preferable. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in the range of 2 nm or more and 3 × 10 ³ nm or less as the pore radius.

The clay and clay mineral used in the present invention can be subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, causing a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.
The ion-exchangeable layered compound used in the present invention can also obtain a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. . Here, the bulky ions play a pillar-like role to support the layered structure and are called pillars. Introducing another substance (guest compound) between layers of a layered substance is called intercalation.

Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; Ti {O (R ¹³ )} ₄ , Zr {O (R ¹³ )} ₄ , PO {O (R ¹³ )} ₃ , B {O (R ¹³ )} ₃ , (R ¹³ is a hydrocarbon group) and other metal alcoholates; [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [ Examples thereof include metal hydroxide ions such as Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more.
When these compounds are intercalated, Si {O (R ¹³ )} ₄ , Al {O (R ¹³ )} ₃ , Ge {O (R ¹³ )} ₄ (R ¹³ is a hydrocarbon group) Polymers obtained by hydrolyzing metal alcoholates such as colloids, colloidal inorganic compounds such as SiO _2, etc. can also coexist. Other examples of pillars include oxides generated by heat dehydration after intercalation of the hydroxide ions between layers.
The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or after being subjected to treatment such as pulverization and sieving by a ball mill. Further, it may be used after water is newly added and adsorbed, or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types. Among these, preferred is clay or clay mineral, and particularly preferred is montmorillonite.

Furthermore, in the present invention, a compound represented by the following formula (3) is preferable as the activating compound (E-1).
[A−H] ^{k +} [M ³ _m (Q ¹ ) _n ] ^k− (3)
(In the formula, [A-H] ^{k +} represents a proton-donating Bronsted acid, wherein A represents a neutral Lewis base, k is an integer of 1 to 7, and [M ³ _m (Q ¹ ) _n ] ^k- represents a compatible non-coordinating anion, provided that M ³ represents a metal or metalloid belonging to the group consisting of groups 5 to 15 of the periodic table, and Q ¹ represents each Independently, hydride, halide, dihydrocarbyl amide group having 2 to 20 carbon atoms, hydrocarbyloxy group having 1 to 30 carbon atoms, hydrocarbon group having 1 to 30 carbon atoms, and 1 to 40 carbon atoms Selected from the group consisting of substituted hydrocarbon groups, provided that the number of Q ^{1 as} a halide is 1 or less, m is an integer of 1 to 7, and n is an integer of 2 to 14. k is as defined above, and nm = k.)

In the present invention, a compound represented by the following formula (13) is preferred as the activating compound (E-1).
^{[A-H] k + [} M 3 m (Q 1) y (G z (T-H) aa) ab] k- (13)
(Wherein [A−H] ^{k +} , A, and k are as defined in the above formula (3), and [M ³ _m (Q ¹ ) _y (G _z (T−H) _aa ) _ab ] ^k− is a compatible non-coordinating anion, M ³ and Q ¹ are as defined in the above formula (3), and G is a polyvalent carbon having a valence of aa + 1 bonded to boron and T. A hydrogen group, T is O, S, NR ¹⁴ , or PR ¹⁴ , wherein R ¹⁴ is a hydrocarbyl, trihydrocarbylsilyl group, trihydrocarbylgermanium group, or hydrogen;
m is as defined in Equation (3) above,
y is an integer from 0 to 7,
z is 0 or 1,
aa is an integer of 0 to 3,
ab is an integer of 1 to 8,
k is as defined above,
y + ab-m = k. )

In the present invention, a compound represented by the following formula (14) is more preferable as the activating compound (E-1).
[A−H] ⁺ [B (Q ² ) ₃ Q ³ ] ⁻ (14)
(Wherein [A-H] ⁺ represents a monovalent proton-donating Bronsted acid, A is as defined in the above formula (3),
[B (Q ² ) ₃ Q ³ ] ⁻ is a compatible non-coordinating anion, Q ² is a pentafluorophenyl group, and the remaining one Q ³ is the number of carbons having one OH group as a substituent. 6 or more and 20 or less substituted aryl groups. )

  In the present invention, specific examples of the compatible non-coordinating anion include tetrakisphenyl borate, tri (p-tolyl) (phenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tris (2,4 -Dimethylphenyl) (hydrphenyl) borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethylphenyl) (phenyl) borate, tris (pentafluorophenyl) (cyclohexyl) Borate, tris (pentafluorophenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate Tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (Hydroxyphenyl) borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) ) Borate, tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydride) Roxy-2-naphthyl) borate, and tris (pentafluorophenyl) (4-hydroxyphenyl) borate is preferred.

Examples of other preferred compatible non-coordinating anions include borates in which the hydroxy group of the borate exemplified above is substituted with an NHR ¹⁵ group. Here, R ¹⁵ is preferably a methyl group, an ethyl group or a t-butyl group.
In the present invention, the proton-providing Bronsted acid is preferably a trialkyl group-substituted ammonium cation such as triethylammonium, tripropylammonium, tributylammonium, trimethylammonium, tributylammonium and trioctylammonium, Also, N, N-dialkyl such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium, etc. Anilinium cation is preferred. Furthermore, dialkylammonium cations such as bis- (1-methylethyl) ammonium and dicyclohexylammonium are also preferable, such as triphenylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium. Such triarylphosphonium cations, dimethylsulfonium, diethylfuronium, diphenylsulfonium and the like are also preferable.
In the present invention, these activating compounds (E-1) may be used alone or in admixture of two or more.

Next, the organoaluminum compound (E-2) used in the present invention will be described.
In the present invention, the organoaluminum compound (E-2) is preferably a trialkylaluminum compound such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or tridecylaluminum. Also, reaction products of these trialkylaluminum compounds with alcohols such as methanol, ethanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, such as dimethylmethoxyaluminum, diethylethoxy Aluminum and dibutylbutoxyaluminum are also preferable. The molar ratio of the alkylaluminum to the alcohols in producing the reaction product is preferably such that Al / OH is in the range of 0.3 to 20, more preferably in the range of 0.5 to 5, and 0.8 to 3 The range of is more preferable.
In the present invention, the amount of the organoaluminum compound (E-2) is preferably 0.01 to 1000 times, more preferably 0.1 to 100 times in terms of a molar ratio to the amount of the activating compound (E-1). 0.5 to 10 times is more preferable.

In the present invention, the reaction between the activating compound (E-1) and the organoaluminum compound (E-2) is not particularly limited, and is an aliphatic hydrocarbon such as hexane or heptane, or an aromatic carbon such as benzene or toluene. It can carry out by making it react between room temperature and 150 degreeC in inert reaction media, such as hydrogen. There is no restriction | limiting in particular about the order of reaction, The method of adding organoaluminum compound (E-2) in activated compound (E-1), activated compound (E-1) to organoaluminum compound (E-2) Either a method of adding or a method of adding both at the same time can be used.
In the present invention, the use amount of the activating compound (E-1) is preferably an amount sufficient to activate the transition metal compound (D-1).
In the present invention, when the activating compound (E-1) is an organoaluminum oxy compound, the amount of the activating compound (E-1) used is preferably 10 times the molar equivalent of (D-1) or more than 1000 times. The molar equivalent is not more than 50, and more preferably not less than 50 times the molar equivalent and not more than 500 times the molar equivalent. Further, when the activating compound (E-1) is a compound defined by the general formula (7), it is preferably not less than 0.8 times the molar equivalent of (D-1) and not more than 5 times the molar equivalent. Preferably, it is not less than 1 mol equivalent and not more than 2 mol equivalent.

Next, a method for producing the solid component [A] from the carrier [C], the transition metal compound component [D], and the activator [E] will be described.
In the present invention, the method for producing the solid component [A] from the carrier [C], the transition metal compound component [D], and the activator [E] is not particularly limited, but aliphatic carbonization such as hexane and heptane. It is preferably carried out in an inert reaction solvent such as hydrogen, benzene, toluene and other aromatic hydrocarbons at a temperature between 0 ° C. and 40 ° C. The method of combining the carrier [C], the transition metal compound component [D], and the activator [E] is not particularly limited, but the transition metal compound component [D] and the activator [E] are contacted in advance. Thereafter, a method of contacting the carrier [C] or a method of contacting the carrier [C] and the activator [E] and then contacting the transition metal compound component [D] is preferable. At this time, the contact between the transition metal compound component [D] and the activator [E] is preferably performed in a good solvent for the transition metal compound component [D]. In addition, when the carrier [C] is brought into contact with the transition metal compound component [D] and the activator [E], it is preferably carried out in a poor solvent for the transition metal compound component [D]. Examples of the good solvent for the transition metal compound component [D] include aromatic compounds such as benzene, toluene, and xylene. Examples of the poor solvent include isobutane, pentane, isopentane, hexane, heptane, octane, and decane. And linear or branched hydrocarbon compounds such as dodecane and kerosene.

In the present invention, the amount of each component used and the ratio of the amounts used are not particularly limited, but it is preferable to use a sufficient amount of the activator [E] to activate the transition metal compound component [D]. .
In the present invention, the transition metal compound component [D] is preferably used in an amount of 5 × 10 ⁻⁶ to 10 ⁻² mol, more preferably 10 ⁻⁵ to 10 ⁻³ mol, relative to 1 g of the carrier [C].
In the present invention, the solid component [A] may be prepolymerized with an olefin. In the present invention, when prepolymerization is performed, the amount of the transition metal compound component [D] used may be 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol with respect to 1 g of the carrier [C]. It is preferably 5 × 10 ⁻⁵ to 10 ⁻³ mol. In the present invention, the prepolymerization temperature is not particularly limited, but is preferably -20 to 80 ° C, more preferably 0 to 50 ° C. In the present invention, the prepolymerization time varies depending on the prepolymerization temperature, but is preferably 0.5 hours or more and 100 hours or less, and more preferably 1 hour or more and 50 hours or less. In the present invention, the amount of the polymer produced by the prepolymerization is preferably 0.1 g or more and 500 g or less, more preferably 0.3 g or more and 300 g or less, and further preferably 1 g or more and 100 g per 1 g of the solid component [A]. . The olefin used in the prepolymerization is preferably selected from olefins used in the polymerization described below, and ethylene is particularly preferable.

Next, the liquid component [B] used in the present invention will be described.
In the present invention, the liquid component [B] is a reaction between an organomagnesium compound [G] soluble in a hydrocarbon solvent represented by the following formula (1) and a compound [J] selected from amines, alcohols, and siloxane compounds. Is an organomagnesium compound soluble in a hydrocarbon solvent.
(M ¹ ) _a (Mg) _b (R ¹ ) _c (R ² ) _d (1)
[Wherein M ¹ is a metal atom belonging to Groups 1 to 3 of the Periodic Table, R ¹ and R ² are hydrocarbon groups having 2 to 20 carbon atoms, and a, b, c, d are It is a real number that satisfies the relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ¹ )]
In the present invention, the reaction between the organomagnesium compound [G] and the compound [J] is not particularly limited, but is inert such as aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as benzene and toluene. It is preferable to carry out the reaction in a reaction medium between room temperature and 150 ° C. There is no restriction | limiting in particular about the order of this reaction, The method of adding compound [J] in organomagnesium compound [G], the method of adding organomagnesium compound [G] to compound [J], or both are added simultaneously. Any of the methods are preferred. Although there is no restriction | limiting in particular about the reaction ratio of organomagnesium compound [G] and compound [J], The molar ratio of compound [J] with respect to all the metal atoms contained in liquid component [B] synthesized by reaction is 0. It is preferably 01 to 2, and more preferably 0.1 to 1.

In the present invention, the liquid component [B] may be used alone or in combination of two or more.
In the present invention, the liquid component [B] is used as an impurity scavenger. The liquid component [B] hardly reduces the polymerization activity even at a high concentration, and therefore can exhibit a high polymerization activity in a wide concentration range. For this reason, the polymerization activity of the olefin polymerization catalyst containing the liquid component [B] can be easily controlled.
Although there is no restriction | limiting in particular about the density | concentration of liquid component [B] at the time of using for superposition | polymerization, The molar concentration of all the metal atoms contained in liquid component [B] is 0.001 mmol / liter or more and 10 mmol / liter or less. Preferably, it is 0.01 mmol / liter or more and 5 mmol / liter or less. If it is less than 0.001 mmol / liter, the effect as a scavenger of impurities may not be sufficient, and it is not preferable if it is more than 10 mmol / liter, because the polymerization activity may decrease.

Next, the organomagnesium compound [G] will be described.
The organomagnesium compound [G] is represented by the above formula (1). Note that in the above equation (1) are shown in the form of complex compound soluble organomagnesium hydrocarbon solvent, but all the complex of (R ¹⁾ 2 _Mg, and other metal compounds thereof It is included. The relational expression e × a + 2b = c + d of the symbols a, b, c, and d indicates the stoichiometry between the valence of the metal atom and the substituent.
The hydrocarbon group represented by R ¹ or R ² in the above formula is an alkyl group, a cycloalkyl group or an aryl group, and is a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, or a 1-methyl group. It is preferably a propyl group, a 2-methylpropyl group, a 1,1-dimethylethyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, or a tolyl group, more preferably an alkyl group, and a primary More preferably, it is an alkyl group.
For a> 0, as the metal atom M ¹ is a metal element can be used belonging to periodic table group 1 to 3 and Group 11 to Group 13 the group consisting of Group, for example, lithium, sodium, potassium, Examples include beryllium, zinc, boron, and aluminum, with aluminum, boron, beryllium, and zinc being particularly preferable.

No particular limitation on the molar ratio b / a of magnesium to metal atom M ^1, but preferably in the range of 0.1 to 50 or less, more preferably 0.5 to 10. When a = 0, the organomagnesium compound [G] is preferably an organomagnesium compound that is soluble in a hydrocarbon solvent, and R ¹ and R ^{2 in} the above formula (1) are the three More preferably, it is any one of the two groups (1), (2) and (3).
(1) At least one of R ¹ and R ² is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably R ¹ and R ² both have 4 to 6 carbon atoms, At least one is a secondary or tertiary alkyl group.
(2) R ¹ and R ² are mutually different alkyl groups, preferably R ¹ is an alkyl group having 2 or 3 carbon atoms, and R ² is an alkyl group having 4 or more carbon atoms. Be.
(3) At least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms, preferably R ¹ and R ² are both alkyl groups having 6 or more carbon atoms.

These groups are specifically shown below. Examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (1) include 1-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 1-ethylpropyl group, 1, Examples include 1-dimethylpropyl group, 1-methylpentyl group, 1-ethylbutyl group, 1,1-dimethylbutyl group, 1-methyl-1-ethylpropyl group, and the like, and 1-methylpropyl group is particularly preferable. In (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group and a propyl group, and the ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include butyl group, amyl group, hexyl group, octyl group and the like, and butyl group and hexyl group are particularly preferable. In (3), examples of the alkyl group having 6 or more carbon atoms include a hexyl group, an octyl group, a decyl group, and a phenyl group. An alkyl group is preferred, and a hexyl group is particularly preferred.
In general, increasing the number of carbon atoms in the alkyl group makes it easier to dissolve in a hydrocarbon solvent, but the viscosity of the solution tends to increase, and use of an alkyl group having a longer chain than necessary is not preferable in handling. In addition, although the said organomagnesium compound is used as a hydrocarbon solution, even if a trace amount of complexing agents, such as ether, ester, and amine, are contained or remain in the solution, it can be used without any problem.

Next, the compound [J] will be described.
This compound is a compound belonging to the group consisting of amines, alcohols and siloxane compounds.
In the present invention, the amine compound is not particularly limited, but is preferably an aliphatic, alicyclic or aromatic amine. Specifically, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, aniline, N -Methylaniline, N, N-dimethylaniline, toluidine and the like.
In the present invention, the alcohol compound is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,1-dimethylethanol, pentanol, hexanol, 2-methyl Pentanol, 2-ethyl-1-butanol, 2-ethyl-1-pentanol, 2-ethyl-1-hexanol, 2-ethyl-4-methyl-1-pentanol, 2-propyl-1-heptanol, 2 -Ethyl-5-methyl-1-octanol, 1-octanol, 1-decanol, cyclohexanol, phenol are preferred, 1-butanol, 2-butanol, 2-methyl-1-pentanol and 2-ethyl-1-hexanol Is more preferable.

In the present invention, the siloxane compound is not particularly limited, but a siloxane compound having a structural unit represented by the following formula (15) is preferable.
(In the above formula (15), R ¹⁶ and R ¹⁷ are groups selected from the group consisting of hydrogen or a hydrocarbon group having 1 to 30 carbon atoms and a substituted hydrocarbon group having 1 to 40 carbon atoms. .)

In the present invention, the hydrocarbon group is not particularly limited, but is methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1 -A dimethylethyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group and a vinyl group are preferred. Further, the substituted hydrocarbon group is not particularly limited, but a trifluoropropyl group is preferable.
In the present invention, the siloxane compound can be used in the form of a dimer or higher chain or cyclic compound composed of one type or two or more types of structural units.
In the present invention, as this siloxane compound, symmetrical dihydrotetramethyldisiloxane, hexamethyldisiloxane, hexamethyltrisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, cyclic methylhydropentasiloxane, cyclic dimethyltetrasiloxane , Cyclic methyltrifluoropropyltetrasiloxane, Cyclic methylphenyltetrasiloxane, Cyclic diphenyltetrasiloxane, (Terminal methyl-capped) Methylhydropolysiloxane, Dimethylpolysiloxane, (Terminal-methylcapped) Phenylhydropolysiloxane, Methylphenylpolysiloxane Is preferred.
In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

Next, the olefin polymerization method in the present invention will be described.
Using the olefin polymerization catalyst of the present invention, ethylene is homopolymerized, or ethylene and an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 3 to 20 carbon atoms, general formula CH ₂ ═CHR ¹⁸ (wherein R ¹⁸ is an aryl group having 6 to 20 carbon atoms) and a linear, branched or cyclic diene having 4 to 20 carbon atoms. , And at least one olefin can be copolymerized.
In the present invention, the α-olefin having 3 to 20 carbon atoms includes, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene, and cyclic olefins having 3 to 20 carbon atoms include, for example, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2- Norbornene, tetracyclododecene, and 2-methyl-1.4,5.8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, wherein the general formula CH ₂ = CHR ¹⁸ (wherein R ¹⁸ is an aryl group having 6 to 20 carbon atoms.) the compound represented by, for example, styrene, Binirushi Examples of the linear, branched or cyclic diene having 4 to 20 carbon atoms such as rhohexane include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene. And cyclohexadiene.

By copolymerizing ethylene and the olefin (comonomer), the density and physical properties of the ethylene polymer can be controlled. The polymerization of olefins according to the present invention can be carried out either by suspension polymerization or gas phase polymerization. In the suspension polymerization method, an inert hydrocarbon solvent can be used as a suspension polymerization medium, and the olefin itself can also be used as a solvent. There are no particular limitations on the inert hydrocarbon solvent, but propane, butane, 2-methylpropane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane. Preferred are alicyclic hydrocarbons such as pentane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane. Propane, butane, 2-methylpropane, pentane, hexane, Heptane is particularly preferred. Also, two or more kinds of inert hydrocarbon solvents can be mixed and used.
The method for adding the olefin polymerization catalyst of the present invention to the polymerization vessel is not particularly limited, but a method of adding it to the polymerization vessel as a slurry of the above-mentioned inert hydrocarbon solvent is preferable, butane, 2-methylpropane, pentane. , Hexane, and heptane are more preferable.

In the present invention, the amount of the catalyst added in the polymerization of olefin is not particularly limited, but the polymerization vessel is adjusted so that the weight of the catalyst relative to the weight of the polymer obtained per hour is 0.001 wt% or more and 1 wt% or less. It is preferable to adjust the concentration of the catalyst. The polymerization temperature is not particularly limited, but is preferably 0 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, and preferably 150 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 It is the range below ℃. Although there is no restriction | limiting in particular in superposition | polymerization pressure, 0.1 MPa or more and 10 MPa or less are preferable, 0.2 MPa or more and 5 MPa are more preferable, 0.5 MPa or more and 3 MPa or less are more preferable. There is no restriction | limiting in particular about the form of this polymerization reaction, Any method of a batch type, a semi-continuous type, and a continuous type can be performed preferably. It is also possible to carry out the polymerization in two or more stages having different reaction conditions.
The molecular weight of the olefin polymer obtained in the present invention can also be adjusted by changing the concentration of hydrogen in the polymerization vessel or the polymerization temperature, as described in DE31273133.2.
By the polymerization method of the present invention, it is possible to produce an olefin polymer having excellent powder properties. Specifically, since the polymer is obtained in the form of a powder not only having a narrow particle size distribution range but also having a high bulk density, the resulting polymer exhibits excellent fluidity.
Next, the present invention will be described more specifically based on examples and the like, but the present invention is not limited to these examples and the like.

In the present invention, hydrogen, nitrogen, and hexane used in Examples and Comparative Examples were dehydrated using MS-13X (manufactured by Showa Union), and hexane was further deoxygenated by performing vacuum degassing using a vacuum pump. Used later. Ethylene, hexane, and 1-hexene used in Examples and Comparative Examples were dehydrated using MS-3A (manufactured by Showa Union), and hexane and 1-hexene were further degassed by vacuum degassing using a vacuum pump. Used after oxygen.
The saturated adsorption amount of the Lewis acidic compound in the examples is as follows: the surface of the precursor of the support [C] is stirred at 20 ° C. with stirring in 80 ml of a 50 g / l hexane slurry of the support [C] under a nitrogen atmosphere. The Lewis acidic compound having a molar number 1.4 times the total molar amount of surface hydroxyl groups contained in the entire slurry calculated from the amount of hydroxyl groups was added and reacted for 2 hours, and then Lewis in the supernatant of the slurry It was calculated from the molar decrease amount of the acidic compound.

The molar amount of the surface hydroxyl group of the precursor of the carrier [C] in the examples was measured by reacting ethoxydiethylaluminum with the surface hydroxyl group of the precursor of the carrier [C] to generate ethane gas and using a gas burette. Calculated from the amount of ethane gas.
The specific surface area of the precursor of the carrier [C] in the examples was measured by the BET method using an autosorb 3MP apparatus manufactured by Yuasa Ionics, using nitrogen as an adsorption gas. The average particle diameter of the precursor of the carrier [C] in the examples was measured using SALD-2100 manufactured by Shimadzu Corporation.
The catalyst activity in the examples represents the amount of polymer produced per hour (g) per gram of Ti atom contained in the solid component [A]. The melt flow rate (MFR) of the polymer in the examples was measured according to JIS K7120 at a temperature of 190 ° C. and a load of 2.16 kg. The density in the examples was measured by the density gradient tube method of JIS K7112. The bulk density in the examples was measured according to JIS K-6721 after the obtained powder was dried at 90 ° C. for 1 hour. Evaluation of the adhesion of the polymer to the polymerization vessel is a measure of the stable operability at the time of scale-up. The evaluation was “◯” when there was no adhesion of the polymer to the polymerization vessel, and “X” when there was even a slight adhesion.

[Example 1]
(Measurement of saturated adsorption amount of Lewis acidic compound to carrier [C] precursor)
Silica Q6 [manufactured by Fuji Silysia] was used as a precursor of the carrier [C]. Triethylaluminum was used as the Lewis acidic compound.
Silica Q6 was heat-treated at 400 ° C. for 5 hours under a nitrogen atmosphere. Silica Q6 after the heat treatment had a specific surface area of 480 m <2> / g and an average particle size of 9.5 [mu] m. The amount of the surface hydroxyl group of the silica after the heat treatment was 1.85 mmol / g. Under a nitrogen atmosphere, 4 g of the silica after the heat treatment was added to a 0.2 L glass container, and 80 ml of hexane was added and dispersed to obtain a silica slurry. 10 ml of a hexane solution (concentration 1M) of triethylaluminum was added to the obtained slurry at 20 ° C. with stirring, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica. As a result of quantifying the amount of aluminum in the supernatant of this hexane slurry, the saturated adsorption amount of triethylaluminum on silica Q6 was 2.1 mmol / g.

(Preparation of carrier [C])
Silica Q6 (40 g) after heat treatment was dispersed in 800 ml of hexane in a 1.8 L autoclave purged with nitrogen to obtain a slurry. While maintaining the resulting slurry at 20 ° C. with stirring, 80 ml of a hexane solution of triethylaluminum (concentration: 1M) was added, followed by stirring for 2 hours to prepare 880 ml of a hexane slurry of carrier [C] adsorbing triethylaluminum.
(Preparation of transition metal compound component [D])
As the transition metal compound (D-1), [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter abbreviated as “titanium complex”). )It was used. As the organomagnesium compound (D-2), the composition formula AlMg ₆ (C ₂ H ₅ ) ₃ (C ₄ H ₉ ) ₁₂ (hereinafter abbreviated as “Mg 1”) was used. This Mg1 was synthesized by mixing a predetermined amount of triethylaluminum and dibutylmagnesium at 25 ° C. in hexane.
200 mmol of titanium complex is dissolved in 1000 ml of Isopar E (Exxon Chemical Co., Ltd.), 20 ml of hexane solution of Mg1 (concentration 1M) is added, hexane is further added to adjust the titanium complex concentration to 0.1M, and the transition metal compound component [ D] was obtained.

(Preparation of activator [E])
As the activating compound (E-1), bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) was used. Ethoxydiethylaluminum was used as the organoaluminum compound.
5.7 g of borate was added and dissolved in 50 ml of toluene to obtain a 100 mM toluene solution of borate. To this toluene solution of borate, 5 ml of hexane solution of ethoxydiethylaluminum (concentration 1M) was added at 25 ° C., and further hexane was added to adjust the borate concentration in the toluene solution to 80 mM. Then, activator [E] was prepared by stirring at 25 degreeC for 1 hour.

(Preparation of solid component [A])
50 ml of the activator [E] obtained by the above operation was added to 880 ml of the slurry of the carrier [C] obtained by the above operation while stirring at 20 ° C., and the reaction was continued for 10 minutes. Next, 40 ml of the transition metal compound component [D] obtained by the above operation was added with stirring, and the reaction was continued for 3 hours to prepare a solid component [A]. At this time, coloring was not recognized by the supernatant liquid of the slurry of solid component [A].
(Preparation of liquid component [B])
The above Mg1 was used as the organomagnesium compound [G]. Methyl hydropolysiloxane (viscosity 20 centistokes at 25 ° C.) was used as the compound [J].
To a 200 ml flask, 40 ml of hexane and Mg1 and 37.8 mmol of Mg and Al as a total amount were added with stirring, and 40 ml of hexane containing 2.27 g (37.8 mmol) of methylhydropolysiloxane was stirred at 25 ° C. Then, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours with stirring to prepare liquid component [B].

(Copolymerization of ethylene and 1-butene)
800 ml of hexane was placed in an autoclave having a capacity of 1.8 l, and 0.2 mmol of the above liquid component [B] was added as the total amount of Mg and Al. Pressurized ethylene was added to the autoclave to increase the internal pressure of the autoclave to 1 MPa, and 3.5 ml of 1-butene was added to the autoclave. Next, the internal temperature of the autoclave was increased to 75 ° C., and the slurry of the solid component [A] obtained above was added to the autoclave so that the weight of the solid component [A] was 8 mg, whereby ethylene and 1- Copolymerization with butene was started. Copolymerization was carried out for 60 minutes while adding ethylene to the autoclave so that the internal pressure of the autoclave was maintained at 1 MPa. After completion of the copolymerization, the reaction mixture (copolymer slurry) was extracted from the autoclave, and the catalyst was deactivated with methanol. Thereafter, the reaction mixture was filtered, washed and dried to obtain 150 g of a dry powder of copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 5100 kg / g-Ti / hr. The copolymer obtained had an MFR of 4.7 g / 10 min and a density of 943 kg / m ³ . The resulting copolymer powder had a bulk density of 0.39 g / cm ³ and exhibited excellent fluidity. These results are shown in Table 1.

[Comparative Example 1]
(Preparation of carrier [C])
The same support [C] precursor as in Example 1 was used. Silica Q6 (40 g) after heat treatment was dispersed in 800 ml of hexane in a 1.8 L autoclave purged with nitrogen to obtain a slurry. While maintaining the resulting slurry at 20 ° C. with stirring, 84 ml of hexane solution of triethylaluminum (concentration 1M) was added, and then stirred for 2 hours to prepare 880 ml of hexane slurry of carrier [C] adsorbed with triethylaluminum. did.
Thereafter, the solid component [A] was prepared in the same manner as in Example 1. At this time, brown coloring was observed in the supernatant of the slurry.
(Copolymerization of ethylene and 1-butene)
Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 to obtain 130 g of a dry powder of copolymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4420 kg / g-Ti / h. The obtained copolymer had an MFR of 5.0 g / 10 min and a density of 944 kg / m ³ . The resulting copolymer powder had a bulk density of 0.32 g / cm ³ and poor fluidity. These results are shown in Table 1.

[Example 2]
The same support [C] precursor as in Example 1 was used. Silica Q6 (40 g) after heat treatment was dispersed in 800 ml of hexane in a 1.8 L autoclave purged with nitrogen to obtain a slurry. While maintaining the obtained slurry at 20 ° C. with stirring, 76 ml of hexane solution of triethylaluminum (concentration 1M) was added, and then stirred for 2 hours to prepare 880 ml of hexane slurry of carrier [C] adsorbed with triethylaluminum. did.
Thereafter, the solid component [A] was prepared in the same manner as in Example 1. At this time, coloring was not recognized by the supernatant liquid of the slurry.
(Copolymerization of ethylene and 1-butene)
Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 to obtain 140 g of a dry powder of copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4760 kg / g-Ti / h. The copolymer obtained had an MFR of 4.9 g / 10 min and a density of 943 kg / m ³ . The bulk density of the obtained copolymer powder was 0.39 g / cm ³ , and the fluidity was good. These results are shown in Table 1.

[Example 3]
A catalyst was prepared in the same manner as in Example 1 except that an organomagnesium compound represented by the chemical formula Mg (C ₆ H ₁₃ ) ₂ was used as the organomagnesium compound [G]. Polymerization was performed to obtain 145 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4930 kg / g-Ti / hr. The copolymer obtained had an MFR of 4.8 g / 10 min and a density of 943 kg / m ³ . The resulting copolymer powder had a bulk density of 0.39 g / cm ³ and exhibited excellent fluidity. These results are shown in Table 1.

[Example 4]
A catalyst was prepared in the same manner as in Example 1 except that dioctylamine was used as the compound [J], and ethylene and 1-butene were copolymerized to obtain 120 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4080 kg / g-Ti / h. The copolymer obtained had an MFR of 4.6 g / 10 min and a density of 944 kg / m ³ . The resulting copolymer powder had a bulk density of 0.38 g / cm ³ and exhibited excellent fluidity. These results are shown in Table 1.

[Example 5]
A catalyst was prepared in the same manner as in Example 1 except that 2-ethylhexanol was used as compound [J], and ethylene and 1-butene were copolymerized to obtain 130 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4420 kg / g-Ti / h. The obtained copolymer had an MFR of 4.5 g / 10 min and a density of 942 kg / m ³ . The resulting copolymer powder had a bulk density of 0.38 g / cm ³ and exhibited excellent fluidity. These results are shown in Table 1.

[Comparative Example 2]
(Preparation of carrier [C])
The same support [C] precursor as in Example 1 was used. Triethylaluminum was adsorbed on the precursor of the carrier [C] in the same manner as in Example 1 except that the amount of triethylaluminum in hexane (concentration 1M) used was changed to 100 ml. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain 800 ml of a hexane slurry of carrier [C] on which triethylaluminum was adsorbed.

(Preparation of catalyst supported on silica)
It carried out similarly to Example 1 and obtained the hexane slurry of the green solid catalyst. In this case, brown coloring was observed in the supernatant of the slurry. Thereafter, the supernatant liquid in the reaction mixture was removed by decantation to remove unadsorbed borate and titanium complex in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain a hexane slurry of the catalyst supported on silica.
(Copolymerization of ethylene and 1-butene)
Polymerization was evaluated in the same manner as in Example 1 to obtain 45 g of a dry powder of copolymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave. The catalytic activity of the catalyst was 2140 kg / g-Ti. The copolymer obtained had an MFR of 4.9 g / 10 min and a density of 942 kg / m ³ . The resulting copolymer powder had a bulk density of 0.27 g / cm ³ and poor fluidity.

[Comparative Example 3]
(Measurement of saturated adsorption amount of Lewis acidic compound to carrier [C] precursor)
Silica P10 (manufactured by Fuji Silysia) was used as a precursor of the carrier [C]. Triethylaluminum was used as the Lewis acidic compound.
Silica P10 was heat-treated at 400 ° C. for 5 hours under a nitrogen atmosphere. Silica P10 after heat treatment had a specific surface area of 300 m ² / g and an average particle size of 23 μm. The amount of the surface hydroxyl group of the silica after the heat treatment was 1.33 mmol / g. Under a nitrogen atmosphere, 4 g of the silica after the heat treatment was added to a 0.2 L glass container, and 80 ml of hexane was added and dispersed to obtain a silica slurry. 10 ml of a hexane solution (concentration 1M) of triethylaluminum was added to the obtained slurry at 20 ° C. with stirring, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica. As a result of quantifying the amount of aluminum in the supernatant of this hexane slurry, the saturated adsorption amount of triethylaluminum on silica P10 was 1.5 mmol / g.

(Preparation of carrier [C])
Silica P10 (40 g) after heat treatment was dispersed in 800 ml of hexane in a 1.8 L autoclave purged with nitrogen to obtain a slurry. While maintaining the resulting slurry at 20 ° C. with stirring, 54 ml of a hexane solution of triethylaluminum (concentration 1M) was added, and then stirred for 2 hours to prepare 880 ml of a hexane slurry of carrier [C] adsorbing triethylaluminum.
Next, a catalyst was prepared in the same manner as in Example 1, and ethylene / 1-butene copolymerization was performed to obtain 60 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 2040 kg / g-Ti / hr. The obtained copolymer had an MFR of 4.5 g / 10 min and a density of 943 kg / m ³ . The resulting copolymer powder had a bulk density of 0.39 g / cm ³ and exhibited excellent fluidity. These results are shown in Table 1.

[Comparative Example 4]
A catalyst was prepared in the same manner as in Example 1 except that the hexane solution (concentration 1M) of triethylaluminum used for the preparation of the carrier [C] was changed to 67 ml, and ethylene and 1-butene were copolymerized. 30 g of dry powder was obtained. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The catalytic activity of the catalyst was 1090 kg / g-Ti / h. The obtained copolymer had an MFR of 5.0 g / 10 min and a density of 944 kg / m ³ . The bulk density of the obtained copolymer powder was 0.20 g / cm ³ , indicating excellent fluidity.

The olefin polymerization catalyst and the olefin polymerization method of the present invention are applied to olefin suspension polymerization (slurry polymerization) or olefin polymerization in gas phase polymerization, particularly ethylene homopolymerization or ethylene / α-olefin copolymerization. It is possible to produce a polymer with excellent powder properties with very high production efficiency.

Claims (6)

A catalyst for olefin polymerization composed of a solid component [A] and a liquid component [B], wherein the solid component [A] adsorbs a Lewis acidic compound in a range of 0.01 mmol / g to 0.4 mmol / g. A support [C] capable of transition, a transition metal compound component [D] belonging to the group consisting of Groups 3 to 11 of the periodic table and soluble in a hydrocarbon solvent, and a transition metal compound component [D] It is composed of an activator [E] that can form a metal complex having catalytic activity by reaction, and the precursor of the carrier [C] is the second group, the third group, the fourth group of the periodic table. An inorganic solid oxide of an element belonging to the group consisting of Group III, Group 13 and Group 14, having an average particle size of 1 micron or more and 20 microns or less; E. T.A. The specific surface area is 300 m ² / g or more and 600 m ² / g or less, and the transition metal compound [D] includes a transition metal compound (D-1) represented by the following formula (8):
(Wherein M ⁶ is a transition gold selected from the group consisting of titanium, zirconium and hafnium.
A transition metal having a formal oxidation number of +2, +3 or +4, and each R ¹² independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, Represents a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of a cyano group, a halogen atom and a composite group thereof, provided that the substituent R ¹² is a carbon atom having 1 to 8 carbon atoms. When it is a hydrogen group, a silyl group, or a germyl group, in some cases, two adjacent substituents R ¹² are bonded to each other to form a divalent group, and thereby bonded to the two adjacent substituents R ¹² , respectively. To form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring , and each X ⁵ independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 1 or more. 18 or less hydrocarbyloxy groups, charcoal Hydrocarbylamino group having 1 to 18 carbon atoms, silyl group, hydrocarbylamide group having 1 to 18 carbon atoms, hydrocarbyl phosphide group having 1 to 18 carbon atoms, hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite thereof A substituent having 1 or more and 20 or less non-hydrogen atoms selected from the group consisting of a group, provided that in some cases, the two substituents X ⁵ work together to neutralize 4 to 30 carbon atoms Forming a conjugated diene or divalent group,
Y ³ represents —O—, —S—, —NR ¹³ — or —PR ¹³ — , wherein R ¹³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 to 8 carbon atoms. A hydrocarbyloxy group, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof.
Z ² represents Si (R ¹³ ) ₂ , C (R ¹³ ) ₂ , Si (R ¹³ ) ₂ —Si (R ¹³ ) ₂ , C (R ¹³ ) —
C (R ¹³ ) ₂ , C (R ¹³ ) = C (R ¹³ ), C (R ¹³ ) ₂ —Si (R ¹³ ) ₂ , Si (R ¹³ ) ₂ —C (R ¹³ ) ₂ or Ge (R ¹³ ) represents ₂ and x is 1, 2 or 3),
The liquid component [B] is composed of an organomagnesium compound [G] soluble in a hydrocarbon solvent represented by the following formula (1) and a compound [J] selected from amines, alcohols, and siloxane compounds. A catalyst for olefin polymerization.
(M ¹ ) _a (Mg) _b (R ¹ ) _c (R ² ) _d (1)
[Wherein M ¹ is a metal atom belonging to the group consisting of groups 1 to 3 and groups 11 to 13 of the periodic table, and R ¹ and R ² are hydrocarbons having 2 to 20 carbon atoms. A, b, c, d are real numbers satisfying the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ¹ )] The olefin polymerization catalyst according to claim 1, wherein the activating agent [E] contains at least an activating compound (E-1) represented by the following formula (3).
[A−H] ^{k +} [M ³ _m (Q ¹ ) _n ] ^k− (3)
(In the formula, [A-H] ^{k +} represents a proton-donating Bronsted acid, wherein A represents a neutral Lewis base, k is an integer of 1 to 7, and [M ³ _m (Q ¹ ) _n ] ^k- represents a compatible non-coordinating anion, provided that M ³ represents a metal or metalloid belonging to the group consisting of groups 5 to 15 of the periodic table, and Q ¹ represents each Independently, hydride, halide, dihydrocarbyl amide group having 2 to 20 carbon atoms, hydrocarbyloxy group having 1 to 30 carbon atoms, hydrocarbon group having 1 to 30 carbon atoms, and 1 to 40 carbon atoms Selected from the group consisting of substituted hydrocarbon groups, provided that the number of Q ^{1 as} a halide is 1 or less, m is an integer of 1 to 7, and n is an integer of 2 to 14. k is as defined above, and nm = k.) The transition metal compound component [D] is a transition metal compound (D-1) represented by the above formula ( 8 ) and an organomagnesium compound (D-2) soluble in a hydrocarbon solvent represented by the following formula (4) The catalyst for olefin polymerization according to claim 1 or 2 , wherein the catalyst for olefin polymerization is a mixture thereof.
(M ⁴ ) _p (Mg) _q (R ³ ) _r (R ⁴ ) _s (OR ⁵ ) _t (4)
[Wherein, M ⁴ is a metal atom belonging to the group consisting of Groups 1 to 3 and Groups 11 to 13 of the Periodic Table;
R ³ , R ⁴ and R ⁵ are hydrocarbon groups having 2 to 20 carbon atoms,
p, q, r, s, and t are numbers satisfying the following relationship.
0 ≦ p, 0 <q, 0 ≦ r, 0 ≦ s, 0 ≦ t, r + s> 0, 0 ≦ t / (r + s) ≦ 2, p × u + 2q = r + s + t (where u is the valence of M ⁴ ) ] The activator [E] is a mixture of an activated compound (E-1) represented by the above formula (4) and an organoaluminum compound (E-2). The olefin polymerization catalyst according to claim 3 . The liquid component [B] is composed of an organomagnesium compound [G] soluble in a hydrocarbon solvent represented by the following formula (1) and a compound [J] selected from amines, alcohols, and siloxane compounds. The olefin polymerization catalyst according to any one of claims 1 to 4 .
(M ¹ ) _a (Mg) _b (R ¹ ) _c (R ² ) _d (1)
[Wherein, M ¹ is a metal atom belonging to the group consisting of lithium, sodium, potassium, beryllium, zinc, boron and aluminum, R ¹ and R ² are hydrocarbon groups having 2 to 20 carbon atoms, a , B, c, d are real numbers satisfying the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ¹ )] An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 5 .