JP2002179723A - Catalyst for olefin polymerization and method for polymerizing olefin using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization capable of producing polymer powder having outstanding powder properties without causing fouling phenomenon to the reactor during polymerization as for suspension polymerization (slurry polymerization) or gas phase polymerization of olefin at high activity, effectively and efficiently, thus realizing continuous operation of a commercial plant, and to provide a method for olefin polymerization using the catalyst. SOLUTION: This catalyst for olefin polymerization is formed by [A] a solid component substantially containing no hydroxy group, [B] a soluble transition metal compound selected from 3rd to 11th families of the periodical table, [C] an activator compound capable of forming a metal complex having catalytic activity by reacting with the transition metal compound [B], and [D] a solid component substantially containing a hydroxy group. The method for olefin polymerization uses the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst for olefin polymerization and a method for olefin polymerization using the catalyst. Specifically, it can be applied to olefin suspension polymerization (slurry polymerization) or gas phase polymerization, and can produce a polymer having excellent powder properties, such as adhesion of a polymer to a reactor during polymerization. The present invention provides a catalyst for olefin polymerization, particularly a catalyst for ethylene polymerization, which does not cause the above-mentioned problems and can realize continuous operation of a commercial plant, and a method for polymerizing ethylene using the catalyst.

[0002]

2. Description of the Related Art As a catalyst for producing an olefin polymer or copolymer, a so-called Ziegler-Natta type catalyst comprising a titanium compound and an organoaluminum compound has been known. On the other hand, in recent years, upon homopolymerization of ethylene or copolymerization of ethylene with another α-olefin,
A technique for polymerizing with high activity by using a catalyst comprising a soluble halogen-containing transition metal compound such as bis (cyclopentadienyl) zirconium dichloride and an aluminoxane, which is one of organic aluminum oxy compounds, has been found. The details of this technique are described in Japanese Patent Publication No. 4-12283 (corresponding to DE 3127133.2).

On the other hand, other than organic aluminum oxy compounds
Taube et al., J. Orga
nometall. Chem., 347.C9 (1988)_Two TiMe (T
HF)]⁺ [BPh_Four ]^- (Cp: cyclopentadienyl
Group, Me: methyl group, Ph: phenyl group, THF: te
Using a compound represented by trihydrofuran)
Polymerisation. Jordan et al., J. Am. Chm. Soc., 10
9.4111 (1987) [Cp _Two ZrR (L)]⁺ (R: methyl
Or a benzyl group, L: Lewis base)
Reports that conium complexes polymerize ethylene.
You.

[0004] Further, Japanese Patent Application Laid-Open Nos. 1-501950 and 1-502036 disclose a catalyst comprising a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. Discloses a method for polymerizing an olefin using In addition, a catalyst system using an organoaluminum compound and a clay, a clay mineral or an ion-exchange layered compound as an activator is disclosed in JP-A-5-301917 and JP-A-6-301917.
It is disclosed in JP-A-136047, JP-A-9-59310, JP-A-11-269222 and the like.

However, these catalyst systems proposed in the prior art are often soluble in the reaction system, and accordingly, the olefin polymer obtained by slurry polymerization or gas phase polymerization is The particle shape is irregular, the bulk density is small, the particle properties are extremely poor, such as many fine powders,
The polymer adheres to the wall surface of the reactor, the stirring blade, and the like, and there is a problem that it cannot be used industrially as it is. Therefore, the production process is usually limited to the solution polymerization method.However, in the case of the solution polymerization method, when an attempt is made to produce a polymer having a high molecular weight, the viscosity of the solution containing the polymer becomes extremely high, and the productivity is greatly increased. However, this method is not preferable in terms of cost, and has a serious problem in industrial application.

In order to solve the above-mentioned problems, a suspension polymerization method using a catalyst in which at least one component of a transition metal compound and an activator is supported on a porous inorganic oxide carrier such as silica, alumina and silica-alumina. Alternatively, attempts have been made to polymerize olefins in a gas phase polymerization method. For example, JP-A-7-268014 discloses a method in which a metallocene compound containing an electron-donating group is used as a transition metal compound, and the metal particle is firmly supported on a solid particle carrier having a Lewis acidic component supported on an inorganic carrier. I have. Furthermore, EP 293815 describes the fixation of metallocenes by the reactivity of hydroxy groups on the surface of inorganic oxides with alkoxysilane functions.

On the other hand, JP-A-8-127611 discloses an example of using a novel boron-containing compound in which a carbon-carbon double bond is incorporated in a molecule as a functional group capable of forming a coordination bond and polymerizing. In JP-A-8-291202,
JP-A-11-12312 discloses an example of chemically fixing a cation component of an ionic compound which becomes a stable anion by reacting with a reaction product of a metallocene compound and an organometallic compound. A catalyst system comprising a solid catalyst component in which an ionic compound is chemically supported on a carrier and a transition metal compound and an organometallic compound is shown.

However, in these methods, the yields obtained in the production of transition metal compounds and ionic compounds are low, and the catalyst components cannot be supported on the carrier sufficiently firmly. There is a disadvantage that the catalyst component is gradually released from the carrier, and the polymer due to the free catalyst component adheres to a wall surface, a stirring blade, a baffle, and the like in the reactor, so that industrial continuous operation cannot be performed. Therefore, it was hard to say that it was a practically effective method.

JP-A-9-194520 discloses a transition metal compound belonging to Groups 4 to 6 of the periodic table, a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex, and an organoaluminum. A method is described in which an olefin is prepolymerized in a catalyst system composed of a compound, and a main polymerization mainly composed of olefin is performed using the obtained granular prepolymerization catalyst. JP-A-9-272713 discloses an olefin polymerization catalyst obtained by prepolymerizing an olefin to a catalyst component comprising a particulate carrier, a transition metal compound of Groups 8 to 10 of the periodic table, and an organometallic compound. ing.

These methods improve the powder properties of the polymer by performing prepolymerization, and deactivate the catalyst over time by protecting the catalyst formed from the transition metal compound and the activator with the prepolymerized polymer. Although it was expected to prevent the occurrence of such a problem, although some effects were observed in improving the properties of the polymer, it was still insufficient. Further, since an extra step of pre-polymerization is required, there are problems that the factors of quality variation increase and the cost becomes disadvantageous. As described above, in the prior art, in a suspension polymerization (slurry polymerization) or a gas phase polymerization of an olefin, a polymer having an excellent powder property cannot be polymerized without causing the polymer to adhere to a reactor. was there.

As a method for preventing fouling in which a polymer adheres to a vessel wall of a reactor, Japanese Patent Application Laid-Open No. 9-12473 is disclosed.
No. 2 discloses that at least about 0.3 wt% of an inert particulate material, such as carbon black, having an average particle size in the range of about 0.1 to 10 microns, based on the total weight of the polymer produced. A method of mixing by volume is shown. However, although fouling is somewhat improved by these methods, it is still insufficient and further improvement is desired.

[0012]

Accordingly, the development of a novel catalyst system capable of polymerizing a polymer having excellent powder properties without causing the catalyst component to be released from the carrier during the polymerization without causing the polymer to adhere to the reactor. Thus, the present invention provides a novel catalyst for olefin polymerization that enables continuous operation of such a commercial plant, and a method for polymerizing olefins using the same.

[0013]

Means for Solving the Problems In view of such a situation, the present inventors have developed a polymer powder which is free from phenomena such as adhesion to a reactor during polymerization and has excellent powder properties. The inventors of the present invention have conducted intensive studies to find a method capable of producing the compound with high activity, effectively and efficiently. That is, the present invention provides: 1) [A] a solid component having substantially no hydroxyl group,
[B] a soluble transition metal compound selected from Groups 3 to 11 of the periodic table, [C] an activator compound capable of reacting with the transition metal compound [B] to form a metal complex having catalytic activity, And [D] a solid component substantially having a hydroxyl group.

2) The solid component [D] substantially having a hydroxyl group is silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide, The olefin polymerization catalyst according to 1), which is at least one substance selected from the group consisting of thorium oxide, a mixture thereof, and a composite oxide. 3) The solid component [D] having substantially hydroxyl groups may have 0.05 to 10 mmol of hydroxyl groups per gram by heating the solid component described in claim 2 at 150 ° C. or more. And at least 0.01 times the molar amount of the hydroxyl groups present on the surface of the solid component,
The olefin polymerization catalyst according to 1) or 2), which is obtained by a method of treating a solid component using an organometallic compound in an amount less than twice the molar amount.

4) The method according to any one of 1) to 3), wherein the soluble transition metal compound [B] selected from Groups 3 to 11 of the periodic table is represented by the following formula (1). Olefin polymerization catalyst. LjWkMXpX'q (1) (wherein, L independently comprises a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group Represents an η-binding cyclic anion ligand selected from the group;
Having up to 8 substituents, each of which independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and 1 to 12 carbon atoms.
A halogen-substituted hydrocarbon group, 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, a hydrocarbylphosphino group having 1 to 12 carbon atoms, silyl Group, aminosilyl group, a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group,

M has a formal oxidation number of +2, +3 or +4
Represents a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table, wherein the transition metal is η ⁵ bonded to at least one ligand L, and W represents up to 50 non-hydrogen atoms. A divalent substituent having a monovalent valence bonded to L and M, respectively, and thereby forming a metallocycle in cooperation with L and M; Are each independently a monovalent anionic σ-binding ligand, a divalent anionic σ-binding ligand divalently bonded to M, and L and M
And a divalent anionic σ, each of which has a monovalent valence
Selected from the group consisting of bonded ligands, represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms,
X ′ each independently represents a neutral Lewis base coordinating compound having up to 40 non-hydrogen atoms,

J is 1 or 2, provided that when j is 2, two ligands L may be bonded to each other via a divalent group having up to 20 non-hydrogen atoms. The divalent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms,
A hydrocarbyleneoxy group of 12, a hydrocarbyleneamino group having 1 to 12 carbon atoms, a silanediyl group, a halosilanediyl group, and a silyleneamino group; k is 0 or 1; , 1 or 2
Provided that X is a monovalent anionic σ-bonded ligand,
Alternatively, in the case of a divalent anionic σ-bonded ligand bonded to L and M, p is an integer smaller by 1 or more than the formal oxidation number of M, and X is bonded only to M. In the case of a divalent anionic σ-bonded ligand, p is an integer smaller than the formal oxidation number of M by (j + 1) or more, and q is 0, 1
Or 2).

5) The activator compound [C] capable of forming a metal complex having catalytic activity by reacting with the transition metal compound [B] is represented by the following formula (2): The catalyst for olefin polymerization according to any one of claims 1) to 4). ^{[L-H] d + [} MmQp] d - (2) ( wherein represents the [L-H] d ⁺ proton donating Bronsted acid, where, L represents a neutral Lewis base, d
Is an integer of 1 to 7; [Mm ⁺ Qp] d ^- represents a compatible non-coordinating anion, wherein M is a metal or metalloid belonging to any of Groups 5 to 15 of the periodic table Wherein Q is independently hydride, halide, dihydrocarbylamide group having 2 to 20 carbon atoms, 1 to 30 carbon atoms.
Is selected from the group consisting of a hydrocarbyloxy group, a hydrocarbon group having 1 to 30 carbon atoms, and a substituted hydrocarbon group having 1 to 40 carbon atoms, provided that the number of halide Q is 1 or less, and m Is an integer from 1 to 7, p is an integer from 2 to 14, d is as defined above, and pm = d. )

6) Reacts with a solid component [A] having substantially no hydroxyl group, a soluble transition metal compound [B] selected from Groups 3 to 11 of the periodic table, and a transition metal compound [B] to increase the catalytic activity. A mixture obtained by pre-contacting an activator compound [C] capable of forming a metal complex having the same with a solid component [D] substantially having a hydroxyl group in an equivalent amount or less. The olefin polymerization catalyst according to any one of 1) to 5), characterized in that: 7) A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to any one of 1) to 6). It is.

According to one embodiment of the present invention, the solid component [A] having substantially no hydroxyl group, the soluble transition metal compound [B] selected from Groups 3 to 11 of the periodic table, and the transition metal compound [B] And an activator compound [C] capable of forming a metal complex having catalytic activity and a solid component [D] substantially having a hydroxyl group. An olefin polymerization catalyst is provided.

In such an olefin polymerization catalyst, since the release of the catalyst component from the carrier during the polymerization is completely suppressed, a phenomenon such as adhesion of the polymer to the reactor does not occur, and the catalyst is obtained as a powder. It is excellent in powder properties such as polymer fluidity and packing density, and is an industrially extremely effective and useful catalyst. Further, if the olefin polymerization catalyst of the present invention is used for ethylene polymerization, an ethylene polymer having excellent powder properties such as fluidity and packing density can be obtained, so that stirring in the reactor can be efficiently performed. In addition, the heat of polymerization can be effectively removed, and an improvement in productivity can be expected.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The solid component [A] having substantially no hydroxyl group used in the present invention is a solid material [hereinafter, referred to as “component [A]”.
Of the precursor of the component [A]. The solid component [D] substantially having a hydroxyl group used in the present invention can be obtained by performing a treatment for removing a part of the hydroxyl group from the surface of the precursor of the component [A].

Examples of the precursor of component [A] include a porous polymer material (provided that the matrix is, for example, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethylene-vinyl ester copolymer, styrene-divinyl Benzene copolymers, polyolefins such as partially or completely saponified ethylene-vinyl ester copolymers or modified products thereof, polyamides, polycarbonates, thermoplastic resins such as polyesters, phenolic resins,
Epoxy resins, urea resins, thermosetting resins such as melamine resins, etc.), inorganic solid oxides of elements belonging to groups 2 to 4, 13 or 14 of the periodic table (for example, silica, alumina, magnesia, magnesium chloride, Zirconia, titania, boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide, thorium oxide, a mixture thereof, or a composite oxide thereof. Examples of the composite oxide containing silica include a composite oxide of silica and an oxide of an element selected from Group 2 or Group 13 of the periodic table, such as silica-magnesia and silica-alumina. Can be In the present invention, the precursor of the component [A] is silica, alumina, or silica, and is mixed with Group 2 or 13 of the periodic table.
It is preferable to be selected from a composite oxide with an oxide of an element selected from elements belonging to the group III. Among these inorganic solid oxides, silica is particularly preferred.

There is no particular limitation on the shape of the silica product used as a precursor of the component [A].
Any shape such as a granular shape, a spherical shape, an aggregated shape, and a fume shape may be used. Preferred examples of commercially available silica products include SD3216.10, SP-9-10046, Davison Syloid ™ 245,
Davison 948 or Davison 952 [all above, Grace Davison (branch of WR Davison (USA))
AEROSIL 812 [manufactured by Degusa AG (Germany)], ES70X [manufactured by Crossfield (USA)],
P-6 and P-10 [manufactured by Fuji Silysia Ltd. (Japan)] and the like.

The component [A] or [D] used in the present invention, E. FIG. T. (Brunauer-Emm
The specific surface area determined by the nitrogen gas adsorption method according to Ett-Teller) is preferably 10 to 1,000 m ² / g.
And more preferably 100 to 600 m ² / g. One of the representative examples of the component [A] or [D] having such a high specific surface area is a component including a porous material having many pores. In the present invention, the pore volume of the component [A] or [D] determined by the nitrogen gas adsorption method is usually preferably 5 cm ³ / g or less, more preferably 0.1 to ³ cm ³ / g.
3 cm ³ / g, more preferably 0.2 to ² cm ³
/ G.

The average particle size of the component [A] or [D] used in the present invention is not particularly limited. The average particle size of the component [A] or [D] is usually 0.5 to 500.
μm is preferred, more preferably 1 to 200 μm, and still more preferably 10 to 100 μm. In the present invention, the component [A] having substantially no hydroxyl group can be obtained by chemically treating the precursor of the component [A] to remove the hydroxyl group from the surface of the precursor of the component [A].

In the present invention, the component [D] substantially having a hydroxyl group is subjected to a chemical treatment of the precursor of the component [A] to remove a part of the hydroxyl group from the surface of the precursor of the component [A]. Can be obtained by: In the present invention,
“The solid component has substantially no hydroxyl group” means that no hydroxyl group is detected on the surface of the solid component (component [A]) by the following method (i) or method (ii).

On the other hand, "the solid component substantially has a hydroxyl group" means that a hydroxyl group is detected on the surface of the solid component (component [D]) by the measurement by the method (i) or the method (ii). means. In the method (i), a predetermined excess amount of dialkylmagnesium is added to a slurry obtained by dispersing the component [A] or [D] in a solvent, and the surface hydroxyl group of the component [A] or [D] is added. Is reacted with a dialkylmagnesium, and then the amount of the dialkylmagnesium remaining unreacted in the solvent is determined in order to determine the amount of the dialkylmagnesium reacted with the surface hydroxyl groups of the component [A] or [D]. After measuring by the method, the initial amount of surface hydroxyl groups of the component [A] or [D] is determined based on the amount of reacted dialkylmagnesium. This method is based on a reaction between a hydroxyl group and a dialkylmagnesium represented by the following reaction formula.

S-OH + MgR ₂ → S-OMgR
+ RH (where S represents a solid material (component [A] or [D]) and R represents an alkyl group). In method (i) and more preferred method (ii), ethoxydiethylaluminum is used instead of dialkylmagnesium. Specifically, in the method (ii), ethoxydiethylaluminum is reacted with the surface hydroxyl group of the component [A] or [D] to generate ethane gas, and the amount of the generated ethane gas is measured using a gas burette. Then, the initial amount of the surface hydroxyl groups of the component [A] or [D] is determined based on the amount of the generated ethane gas.

Further, in the present invention, it is preferable to remove water (crystal water, adsorbed water, etc.) by heating the precursor of component [A]. The heat treatment of the precursor of the component [A]
For example, under an inert atmosphere or a reducing atmosphere, preferably 150 ° C. to 1,000 ° C., more preferably 250 ° C.
The treatment can be performed at a temperature of from 0 to 800 ° C for 1 hour to 50 hours. In the present invention, after dehydration by heat treatment, the precursor of the component [A] is further chemically treated to remove a part or all of the hydroxyl groups from the surface of the precursor of the component [A], and the component [A] or Obtaining component [D] comprises:
More preferred.

As for the chemical treatment for removing a part or all of the hydroxyl groups from the precursor of the component [A], it is recommended to perform a chemical treatment of bringing the precursor of the component [A] into contact with an organometallic compound. You. Examples of the organometallic compound used in the chemical treatment include Group 2 to Period 1 of the periodic table.
Examples include compounds of elements belonging to Group 3 and the like. Particularly preferred among these compounds are organoaluminum or organomagnesium. Examples of preferred organoaluminum compounds used in the chemical treatment of the precursor of component [A] include compounds represented by the following formula (3): AlR _n X _3-n (3) Are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms.
X represents 20 aryl groups, each X independently represents a halide, hydride or an alkoxide group having 1 to 10 carbon atoms, and n is 1, 2 or 3).

The compounds represented by the above formula (3) may be used alone or in combination. Examples of the group R in the formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, and the like. Examples of the group X in the formula (3) include a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, a chlorine atom and the like.

Specific examples of the organoaluminum compound used for the chemical treatment of the precursor of the component [A] include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum. Compounds and the reaction products of these trialkylaluminum compounds with alcohols (eg, methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol).

Examples of such reaction products include methoxydimethylaluminum, ethoxydiethylaluminum, butoxydibutylaluminum and the like.
When producing such a reaction product, the ratio of the trialkylaluminum to the alcohol is preferably in the range of 0.3 to 20 in Al / OH molar ratio,
More preferably, it is in the range of 0.5 to 5, and 0.8 to 5.
More preferably, it is in the range of 3.

In addition, an organic aluminum oxy compound described later as an example of the component [C] can also be used for the chemical treatment of the precursor of the component [A]. Preferred examples of the organomagnesium compound used for the chemical treatment of the precursor of the component [A] include a compound represented by the following formula (4). During _{MgR n X 2-n (4} ) ( wherein, R are each independently a number from 1 to 12 linear, branched or cyclic alkyl group, or a carbon number from 6 to
20 represents an aryl group, X each independently represents a halide, hydride or an alkoxide group having 1 to 10 carbon atoms, and n is 1 or 2.)

The compounds represented by the above formula (4) may be used alone or in combination. Examples of the group R in the formula (4) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, and the like. Examples of the group X in the formula (4) include a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, a chlorine atom and the like.

Specific examples of the organomagnesium compound used for the chemical treatment of the precursor of the component [A] include diethylmagnesium, dibutylmagnesium, butylethylmagnesium, butyloctylmagnesium and the like. When the precursor of the component [A] is chemically treated, the above-mentioned organoaluminum compound or organomagnesium compound may be used in a state where these are mixed. When the component [A] is obtained by chemically treating the precursor of the component [A], the amount of the organometallic compound is equal to or larger than the molar amount of the hydroxyl group present on the surface of the precursor of the component [A]. Used. The amount of the organometallic compound used in the chemical treatment is preferably 1 to 10 times, more preferably 1 to 5 times, the molar amount of the hydroxyl group present on the surface of the precursor of the component [A]. The amount is preferably 1 to 2 times, particularly preferably 1 to 1.5 times, and most preferably 1 to 1.3 times.

When the precursor of the component [A] is chemically treated to obtain the component [D], the amount of the organometallic compound is preferably smaller than the molar amount of the hydroxyl group existing on the surface of the precursor of the component [A]. . In this case, the upper limit of the organometallic compound used is usually preferably less than the equivalent of the molar amount of the hydroxyl group present on the surface of the precursor of the component [A], more preferably 0.9.
The amount is 9 times or less, more preferably 0.9 times or less, and most preferably 0.7 times or less.

It is preferable to adjust the surface hydroxyl groups on the solid component [D] to 0.1 to 5 mmol per 1 g of the solid component by the above treatment. In the present invention, the component [A] is particularly preferably silica having substantially no hydroxyl group. The silica is preferably at least 150 ° C,
More preferably, by heating silica at a temperature of 250 ° C. or higher, the amount of surface hydroxyl groups is preferably obtained by a method of treating silica pretreated to 0.05 to 10 mmol per 1 g of silica with an organometallic compound. Is preferred. As the organometallic compound for treating the silica [precursor of the component [A]], an organoaluminum compound is preferably used, and an organoaluminum compound of the formula (3) is particularly preferred. The amount of the organoaluminum compound used is preferably 1 to 10 times the molar amount of the surface hydroxyl groups of the pretreated silica.

The surface hydroxyl groups of the pretreated silica are 0.1 to 5 mmol per 1 g of the pretreated silica.
Is more preferable, and most preferably 0.5 to 2 mmol. Further, in the present invention, component [D] is preferably silica having substantially hydroxyl groups. By heating the silica at a temperature of preferably 150 ° C. or more, more preferably 250 ° C. or more, the amount of surface hydroxyl groups is 0.05 g / g of silica.
It can be obtained by a method of treating pretreated silica with an organometallic compound to 10 to 10 mmol. As the organometallic compound for treating silica, it is preferable to use an organoaluminum compound, and it is particularly preferable to use the organoaluminum compound of the formula (3).

The surface hydroxyl groups of the above treated silica having substantially hydroxyl groups are 0.1 to 5 m / g of silica.
mol, more preferably 0.3 to 2 mmol
Is most preferred. Next, the soluble transition metal compound [B] selected from Groups 3 to 11 of the periodic table used in the present invention will be described. Examples of the component [B] used in the present invention include a compound represented by the following formula (1).

LjWkMXpX′q (1) (wherein L is each independently a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group Represents an η-binding cyclic anion ligand selected from the group consisting of
Having up to 8 substituents, each of which independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and 1 to 12 carbon atoms.
A halogen-substituted hydrocarbon group, 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, a hydrocarbylphosphino group having 1 to 12 carbon atoms, silyl Group, aminosilyl group, a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group,

M represents a formal oxidation number of +2, +3 or +4
Represents a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table, wherein the transition metal is η ⁵ bonded to at least one ligand L, and W represents up to 50 non-hydrogen atoms. A divalent substituent having a monovalent valence bonded to L and M, respectively, and thereby forming a metallocycle in cooperation with L and M; Are each independently a monovalent anionic σ-binding ligand, a divalent anionic σ-binding ligand divalently bonded to M, and L and M
And a divalent anionic σ, each of which has a monovalent valence
Selected from the group consisting of bonded ligands, represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms,
X ′ each independently represents a neutral Lewis base coordinating compound having up to 40 non-hydrogen atoms,

J is 1 or 2, provided that when j is 2, two ligands L may be bonded to each other via a divalent group having up to 20 non-hydrogen atoms. The divalent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms,
A hydrocarbyleneoxy group of 12, a hydrocarbyleneamino group having 1 to 12 carbon atoms, a silanediyl group, a halosilanediyl group, and a silyleneamino group; k is 0 or 1; , 1 or 2
Provided that X is a monovalent anionic σ-bonded ligand,
Alternatively, in the case of a divalent anionic σ-bonded ligand bonded to L and M, p is an integer smaller by 1 or more than the formal oxidation number of M, and X is bonded only to M. In the case of a divalent anionic σ-bonded ligand, p is an integer smaller than the formal oxidation number of M by (j + 1) or more, and q is 0, 1
Or 2).

Examples of the ligand X in the compound of the formula (1) include a halide, a hydrocarbon group having 1 to 60 carbon atoms, a hydrocarbyloxy group having 1 to 60 carbon atoms, and a 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 coordinating compound X ′ in the compound of the above formula (1) include phosphine, ether, amine, olefin having 2 to 40 carbon atoms, diene having 1 to 40 carbon atoms, and these compounds. Derived divalent groups and the like can be mentioned. Next, examples of the component [B] used in the present invention include a compound represented by the following formula (5).

[0046]

Embedded image

(Wherein R ¹ and R ⁴ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a total of 7 to 2 carbon atoms)
An aromatic group having a hydrocarbon group on the ring 0, R ² and R
³ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ may be bonded to each other to form a ring; and X and Y each independently represent a halogen An atom or a hydrocarbon group having 1 to 20 carbon atoms, M represents nickel or palladium. )).

In the above general formula (5), R ¹ and R ⁴
Among the aliphatic hydrocarbon groups having 1 to 20 carbon atoms,
A linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, sec-butyl group,
tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group,
And cyclooctyl group. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group.

The aromatic group having a hydrocarbon group on a ring having a total of 7 to 20 carbon atoms includes, for example, a linear group having 1 to 10 carbon atoms on an aromatic ring such as a phenyl group or a naphthyl group.
Examples thereof include groups into which one or more branched or cyclic alkyl groups have been introduced. As R ¹ and R ⁴ , an aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropylphenyl group is particularly preferable. R ¹ and R ⁴ may be the same or different.

Further, R ² and R ^{3 have} 1 to 20 carbon atoms.
Examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a 7 to 20 carbon atoms.
Aralkyl groups and the like. Here, carbon number 1
20 linear or branched alkyl groups, 3-20 carbon atoms
Examples of the cycloalkyl group include the same as those exemplified in the description of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ⁴ . Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. And the like.

The R ² and R ³ may be the same or different. Further, they may combine with each other to form a ring. On the other hand, examples of the halogen atom in X and Y include a chlorine, bromine or iodine atom, and the hydrocarbon group having 1 to 20 carbon atoms has 1 to 20 carbon atoms in R ² and R ³ . The hydrocarbon group is as described above. X and Y are particularly preferably a bromine atom or a methyl group. X and Y
May be the same or different.

In the present invention, the component [B] is preferably a transition metal compound represented by the formula (1) (where j = 1). Preferred examples of the compound represented by the formula (1) (where j = 1) include a compound represented by the following formula (6).

[0053]

Embedded image

Wherein M is a transition metal selected from the group consisting of titanium, zirconium and hafnium,
Represents a transition metal having a formal oxidation number of +2, +3 or +4, and R ⁵ is each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, 2 selected from the group consisting of these complex groups
Represents a substituent having up to 0 non-hydrogen atoms, provided that when the substituent R ⁵ is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group, two adjacent substituents may be present. R ⁵ combine with each other to form a divalent group, whereby the ring cooperates with the bond between the two carbon atoms of the cyclopentadienyl ring which are respectively attached to the two adjacent substituents R ^5. To form

X ″ independently represents a halide, 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, -18 hydrocarbyl amide groups, C 1-18 hydrocarbyl sulfide groups,
Represents a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbyl sulfide group having 1 to 18 carbon atoms and a complex group thereof, provided that 2
Two substituents X ″ cooperate to form a neutral conjugated diene or divalent group having 4 to 30 carbon atoms;

Y ′ represents —O—, —S—, —NR ^* — or —PR ^* —, where R ^* is a hydrogen atom, carbon atom 1
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, a halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof; Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂
SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR
^* ₂ or GeR ^* ₂ , where R ^* is as defined above, and n is 1, 2 or 3.

Specific examples of the component [B] used in the present invention include the following compounds.
Bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) ) Neopentyl zirconium 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 (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium di Benzyl, bis (cyclopentadienyl) zirconium dihydride, bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconiumdiethyl, ethylenebis (indenyl) zirconiumdihydride, ethylenebis (4 5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4-methyl-1-indenyl) zirconium dimethyl, ethylenebi (5-methyl-1-indenyl) zirconium dimethyl,

Ethylene bis (6-methyl-1-indenyl) zirconium dimethyl, ethylene bis (7-methyl-1-indenyl) zirconium dimethyl, ethylene bis (5-methoxy-1-indenyl) zirconium dimethyl, ethylene bis (2, 3-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) dimethylzirconium, ethylenebis- (4,7-dimethoxy-1-indenyl) zirconium dimethyl, methylenebis (cyclopentadienyl) ) Zirconium dihydride, methylene bis (cyclopentadienyl) zirconium dimethyl,

Isopropylidene (cyclopentadienyl) zirconium dihydride, isopropylidene (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-fluorenyl)
Zirconium dihydride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dimethyl, silylene bis (cyclopentadienyl) zirconium dihydride, silylene bis (cyclopentadienyl) zirconium dimethyl, dimethyl silylene (cyclopentadienyl) zirconium dihydride, Dimethylsilylene (cyclopentadienyl) zirconium dimethyl, [(Nt-butylamide) (tetramethyl-η
⁵ -cyclopentadienyl) -1,2-ethanediyl]
Titanium dimethyl, [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl,

[(N-methylamide) (tetramethyl-
η^Five-Cyclopentadienyl) dimethylsilane] titani
Dimethyl, [(N-phenylamide) (tetramethyl
Le-η^Five-Cyclopentadienyl) dimethylsilane] di
Titanium dimethyl, [(N-benzylamide) (tetra
Methyl-η^Five-Cyclopentadienyl) dimethylsila
N] titanium dimethyl, [(Nt-butylamide)
(Η^Five-Cyclopentadienyl) -1,2-ethanedii
Ru] titanium dimethyl, [(Nt-butylamide)
(Η^Five-Cyclopentadienyl) dimethylsilane] tita
Dimethyl, [(N-methylamide) (η^Five-Shiku
Lopentadienyl) -1,2-ethanediyl] titanium
Dimethyl, [(N-methylamide) (η ^Five-Cyclope
Nantadienyl) dimethylsilane] titanium dimethyl,
[(Nt-butylamide) (η^Five-Indenyl) dime
Tylsilane] titanium dimethyl, [(N-benzyla
Mid) (η^Five-Indenyl) dimethylsilane] titanium
Dimethyl.

Specific examples of the component [B] used in the present invention further include a “dimethyl” portion of the name of each of the zirconium and titanium compounds mentioned above as a specific example of the component [B] The compound at the end of the compound name, that is, that appears immediately after the portion of "zirconium" or "titanium", which is the name corresponding to the portion of X "in the formula (6) is shown below. Compounds having names that can be used in place of arbitrary ones are also included.

“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 eta ^{4-2,4-hexadiene,} "" s- trans eta ⁴ -1,3-pentadiene "," s- trans eta ^{4-1,4-ditolyl-1,3-butadiene} "
“S-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene”,

[0064] "s- cis -η ⁴ -1,4- diphenyl -
1,3-butadiene, "" s- cis eta ^{4-3-methyl-1,3-pentadiene} "," s- cis eta ^4-1,4
-Dibenzyl-1,3-butadiene "," s-cis-η
^{4-2,4-hexadiene} "," s- cis -η ⁴ -1,3
- pentadiene "," s- cis eta ^{4-1,4-ditolyl-1,3-butadiene,} "" s- cis eta ^4-1,4
-Bis (trimethylsilyl) -1,3-butadiene "
etc.

The transition metal compound [B] used in the present invention can be synthesized by a generally known method. An example of a preferred method for synthesizing the transition metal compound used as the component [B] in the present invention is described in US Pat. No. 5,491,24.
No. 6 can be exemplified. In the present invention, these transition metal compound components [B] may be used alone or in combination.

Next, the activator compound [C] capable of reacting with the transition metal compound [B] to form a metal complex having catalytic activity in the present invention will be described. An example of the component [C] is an organic aluminum oxy compound. 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 water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of the hydrocarbon medium in the above, and reacting the adsorbed water or water of crystallization with the organoaluminum compound.

(2) In a medium such as benzene, toluene, ethyl ether, tetrahydrofuran, etc., water,
A method of applying ice or water vapor. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The organic aluminum oxy compound is
It may contain a small amount of an organometallic component. The solvent or the unreacted organic aluminum compound may be removed from the recovered solution of the organic aluminum oxy compound by distillation, and then redissolved in a solvent or suspended in a poor solvent for the organic aluminum oxy compound. Specific examples of the organoaluminum compound used when preparing the organoaluminum oxy compound include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum,
Trialkyl aluminum such as trioctyl aluminum and tridecyl aluminum,

Trialkylalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminums such as diethylaluminum hydride and diisobutylaluminum hydride Examples include dialkyl aluminum alkoxides such as hydride, dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. In addition, examples of the component [C] include a clay, a clay mineral, and an ion-exchange layered compound. In this case, the organoaluminum compound represented by the above formula (3) is preferably used at the same time. At this time, a trialkyl aluminum is preferably used.

The clay used in the present invention is usually preferably composed mainly of a clay mineral. In the ion-exchange layered compound, the planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force. Compounds having a crystal structure and containing exchangeable ions are preferable. Further, as a clay, a clay mineral or an ion-exchangeable layered compound, hexagonal dense packing type, antimony type, C
Examples thereof include ionic crystalline compounds having a layered crystal structure such as dCl ₂ type and CdI ₂ type. As these clays, clay minerals, and ion-exchangeable layered compounds, not only natural products but also artificial synthetic products can be used.

Specific examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, is like halloysite, the ion-exchange layered compounds, 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 (HPO ₄ ) ₂ , γ-Ti (NH ₄
PO ₄ ) ₂ .H ₂ O and other crystalline acidic salts of polyvalent metals.

From the viewpoint of polymerization activity, such clays, clay minerals, and ion-exchange layered compounds are preferably those having a pore volume of 2 cm or more as measured by a mercury intrusion method and having a pore volume of 0.1 cm ³ / g or more. Those having 0.3 to ⁵ cm ³ / g are particularly preferred. Here, the pore volume was measured by a mercury intrusion method using a mercury porosimeter as a pore radius of 2 to 3 × 1.
It is measured in the range of 0 ³ nm.

The clay or clay mineral used in the present invention can be subjected to a chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of the clay can be used. Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and 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, resulting in a change in the structure of the clay. In salt treatment and organic matter treatment,
Form ion complexes, molecular complexes, organic derivatives, etc.
The surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention utilizes the ion-exchange property to exchange the exchangeable ions between the layers with another large bulky ion, thereby obtaining a layered compound in which the layers are expanded. You can also. Here, the bulky ions play a pillar-like role for supporting the layered structure, and are called pillars. Introducing another substance (guest compound) between layers of the layered substance is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; Ti (OR) ₄ , Zr (OR) ₄ , PO (O
_{R) 3, B (OR)} 3, (R is a metal alcoholate etc.) hydrocarbon _{radical; [Al 13 O 4 (OH} ) 2 4] 7+, [Zr 4 (O
H) ₁₄ ] ²⁺ , and 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 intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , Ge (O
A polymer obtained by hydrolyzing a metal alcoholate such as R) ₄ (R is a hydrocarbon group, etc.), a colloidal inorganic compound such as SiO _2, and the like can also coexist. Other examples of pillars include oxides generated by intercalating the hydroxide ions between layers and then heating and dehydrating.

The clay, clay mineral and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as pulverization by a ball mill and sieving. Further, it may be used after newly adding and adsorbing water or performing a heat dehydration treatment. Further, they may be used alone or in combination of two or more. Among them, preferred are clay or clay mineral, and particularly preferred is montmorillonite.

Further, examples of the component [C] include compounds defined by the following general formula (7). ^{[L-H] d + [} MmQp] d - (7) where a [L-H] d ⁺ proton-imparting Bronsted acid wherein, L is a neutral Lewis base. In the formula, [MmQp] d ⁻ is a compatible non-coordinating anion, M is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is each independently hydride or dialkyl. It is an amide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, a substituted hydrocarbon group having up to 20 carbon atoms, and Q as a halide is one or less.
Further, m is an integer of 1 to 7, p is an integer of 2 to 14, d is an integer of 1 to 7, and pm = d.

In the present invention, a preferable example of the component [C] is represented by the following general formula (8). [MmQn (Gq (T-H ) r) z] d - (8) where, M is a metal or metalloid selected from Group 5 to Group 15 of the periodic table. Q is as defined in the general formula (7), G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to boron and T, and T is O, S, NR, or P
R, where R is a hydrocarbyl, trihydrocarbylsilyl group, trihydrocarbylgermanium group, or hydrogen.

M is an integer of 1 to 7, and n is 0 to
7, q is an integer of 0 or 1, and r is 0 to
3, z is an integer of 1 to 8, d is 1 to 7
And n + z−m = d. A more preferred example of the component [C] of the present invention is represented by the following general formula (9). [LH] ⁺ [BQ ₃ Q ′] ⁻ (9) wherein [LH] ⁺ is a proton-donating Bronsted acid, and L is a neutral Lewis base. In the formula, [BQ ₃ Q ′] ⁻ is a compatible non-coordinating anion,
Is a pentafluorophenyl group, and the other one Q 'is a substituted aryl group having 6 to 20 carbon atoms and having one OH group as a substituent.

Specific examples of the compatible noncoordinating anion of the present invention include, for example, tetrakisphenylborate, 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-hydroxy-2-naphthyl) borate and the like, and most preferably tris (pentafluorophenyl) (4-hydroxyphenyl) borate.

Examples of other preferred compatible non-coordinating anions include those where the hydroxy group of the borate exemplified above is NH
Borates replaced with R groups. here,
R is preferably a methyl, ethyl or t-butyl group. Specific examples of the proton-donating Bronsted acid of the present invention include, for example, triethylammonium, tripropylammonium, tri (n-butyl)
Ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium and the like; and trialkyl group-substituted ammonium cations, and N, N-dimethylanilinium,
N, N-dialkylanilinium cations such as -diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium and the like are also suitable.

Further, dialkylammonium cations such as di- (i-propyl) ammonium and dicyclohexylammonium are also preferable, and triphenylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium are also preferable. Also suitable are triarylphosphonium cations such as chromium, dimethylsulfonium, diethylfluphonium, diphenylsulfonium and the like.

In the present invention, these activator compound components [C] may be used alone or in combination. The catalyst of the present invention is obtained by bringing components [A] to [D] into contact. In the present invention, the method of combining the component [A], the component [B], the component [C], and the component [D] is not particularly limited, but it is preferable that the component [D] is added last. . For example, after the components [B] and [C] are brought into contact in advance, the component [A] is brought into contact with the component [D], or the component [A] is brought into contact with the component [C]. After that, a method of contacting the component [B] and further contacting the component [D] can be adopted, and a polymer having excellent powder properties can be produced by such a method.
It is possible to prevent the polymer from adhering to the reactor during the polymerization.

When such components are contacted, component [B]
And [C] are preferably performed in a good solvent of the component [B]. When the component [A] or the component [D] is brought into contact with the other components [B] and [C], the contact is preferably performed in a poor solvent for the component [B]. Examples of the good solvent for the component [B] include aromatic compounds such as benzene, toluene, and xylene. As the poor solvent for the component [B], for example, isobutane, pentane, isopentane,
Linear or branched hydrocarbon compounds such as hexane, heptane, octane, decane, dodecane, kerosene and the like can be mentioned.

In the present invention, the amounts of the components used and the ratio of the components used are not particularly limited, but it is preferable to use a sufficient amount of the component [C] to react with the component [B]. In the present invention, component [B] is preferably 5 × 10 ⁻⁶ to 10 ⁻² mol, more preferably 10 ⁻⁵ to 1 g per 1 g of component [A].
It is used in an amount of 10 ^-3 mol. In the present invention, the amount of hydroxyl group in the component [D] is preferably 20 times or less, more preferably 10 times or less, particularly preferably 5 times or less the amount of the component [B].

When the components [A], [B] and [C] are brought into contact with each other, depending on the conditions, there may be a part of the unreacted component [B] in the reaction solvent. The unreacted component [B] is removed by a washing method using a soluble solvent, a method of heating and / or a reduced pressure treatment, or the like. In the present invention, the step of removing the unreacted component [B] can be omitted by adding an appropriate amount of the component [D].

The olefin polymerization catalyst of the present invention is
The refin may be pre-polymerized. Prepolymerization smell
Component [B] is preferably 1 g of Component [A].
10x ^-Five~ 5 × 10^ThreeMol, more preferably 5 × 10^-Five
-10^-3Desirably, they are used in molar amounts. Extra weight
The combined temperature is usually preferably -20 to 80 ° C, more preferably
Is in the range of 0 to 50 ° C., and the pre-polymerization time is the pre-polymerization temperature.
Depending on the degree, usually 0.5 to 100 hours is preferred
And more preferably about 1 to 50 hours.

The amount of the polymer produced by the prepolymerization is preferably about 0.1 to 500 g, more preferably 0.3 to 300 g, and particularly preferably 1 to 100 g per gram of the solid component. The olefin used in the prepolymerization is preferably selected from olefins used in the polymerization described below. Of these, ethylene is particularly preferably used.

The olefin polymerization catalyst of the present invention comprises:
It is preferable to add a slurry of an aliphatic hydrocarbon or an alicyclic hydrocarbon, which will be described later, to a polymerization vessel. Next, a specific embodiment in which the polymerization of ethylene is performed in the presence of the catalyst of the present invention will be described. Ethylene is homopolymerized using the olefin polymerization catalyst of the present invention, or ethylene and an α-olefin having preferably 3 to 20 carbon atoms,
To 20 cyclic olefins of the formula CH ₂ ＣＨCHR (where R
Is an aryl group having 6 to 20 carbon atoms. ) And at least one olefin selected from the group consisting of linear, branched or cyclic dienes having 4 to 20 carbon atoms.

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-eicosene, and the cyclic olefin having 3 to 20 carbon atoms includes, for example, cyclopentene, cyclohexene, cycloheptene, norbornene, -Methyl-2
-Norbornene, tetracyclododecene, and 2-methyl-1.4,5.8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene selected from the group consisting of a general formula CH ₂ ＣＨCHR (where R is 6 carbon atoms)
To 20 aryl groups. ) Is, for example, styrene, vinylcyclohexane or the like, and the linear, branched or cyclic diene having 4 to 20 carbon atoms is, for example, 1,3-butadiene, 1,4-pentadiene , 1,5-hexadiene, 1,4-hexadiene, and cyclohexadiene.

Ethylene and the above-mentioned olefins (comonomer)
The density and physical properties of the ethylene polymer can be controlled by copolymerizing with the ethylene polymer. The polymerization of the olefin according to the present invention can be carried out by either a suspension polymerization method or a gas phase polymerization method.
In the suspension polymerization method, an inert hydrocarbon medium can be used as a medium for the suspension polymerization, and the olefin itself can be used as a solvent. Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic rings such as cyclopentane, cyclohexane, and methylcyclopentane. Group hydrocarbons;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene, and dichloromethane; and mixtures thereof.

The feed amount of the catalyst in the polymerization of ethylene using the olefin polymerization catalyst of the present invention is as follows:
For example, it is desirable to adjust the catalyst concentration in the polymerization system so that the amount of the catalyst is 1 wt% to 0.001 wt% with respect to the mass of the polymer obtained per hour. The polymerization temperature is usually preferably 0 ° C. or higher, more preferably 50 ° C.
And more preferably at least 60 ° C.
C. or lower, preferably 110 C. or lower, more preferably 100 C. or lower. The polymerization pressure is
Usually, normal pressure to 10 MPa is preferable, more preferably 0.2 to 5 MPa, and still more preferably 0.5 to 3 MPa.
The polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

Furthermore, for example, DE 3127133.2
As described in, the molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.
In the present invention, the catalyst for olefin polymerization can contain other components useful for olefin polymerization in addition to the above components. Hereinafter, the present invention will be described more specifically with reference to Examples and the like, but the present invention is not limited to these Examples and the like.

[0097]

Example 1 (Preparation of component [A] and component [D]) 1 g
Silica P-10 [Fuji Silysia Ltd. (Japan)]
It was calcined at 400 ° C. for 5 hours in a nitrogen atmosphere and dehydrated. The amount of surface hydroxyl groups of the dehydrated silica is 1.3 mmol / g-S
iO ₂ . 1 g of this dehydrated silica is mixed with 40 m of hexane.
to obtain a slurry. 1.5 ml of a hexane solution of triethylaluminum (concentration: 1 M) was added to the obtained slurry, and the mixture was stirred for 1 hour to react triethylaluminum with the surface hydroxyl groups of the silica. A component [A] in which all surface hydroxyl groups of the triethylaluminum-treated silica were crushed was obtained. Thereafter, unreacted triethylaluminum in the supernatant was removed by removing the supernatant in the obtained reaction mixture by decantation. Thereafter, an appropriate amount of hexane was added to obtain 50 ml of a hexane slurry of silica treated with triethylaluminum. The supernatant removed by decantation was subjected to a test to determine the triethylaluminum content of the supernatant. As a result of the test, the supernatant liquid had a triethylaluminum content of 0.0
It turned out to be 7 mmol.

On the other hand, the same reaction was carried out except that 0.7 ml of a hexane solution of triethylaluminum (concentration: 1 M) was added in the above reaction, to obtain 50 ml of a hexane slurry of the component [D] in which a part of hydroxyl groups remained. . A part of the hexane slurry is taken out, reacted with ethoxydiethylaluminum to generate ethane gas, and the amount of generated ethane gas is measured using a gas burette. When the initial amount of surface hydroxyl groups was determined, it was estimated that 0.53 mmol of hydroxyl groups remained per 1 g of silica.

(Preparation of Catalyst Supported on Silica) Bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as "borate") 1.1
4 g was added to and dissolved in 10 ml of toluene to obtain a 100 mM toluene solution of borate. 1 ml of a 0.1 M toluene solution of ethoxydimethylaluminum was added to this toluene solution of borate at room temperature, and toluene was further added to adjust the borate concentration in the toluene solution to 50 mM. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a reaction mixture containing borate.

1.2 ml of this reaction mixture containing borate
Was added to 50 ml of the slurry of the component [A] obtained above, and the mixture was stirred for 1 hour to carry a borate on silica. Thus, a slurry of borate-supported silica was obtained. [(Nt-butylamide)] was added to the obtained slurry.
(Tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter, referred to as
A solution obtained by dissolving 10 mmol of “titanium complex”) in 100 ml of Isopar E (trade name of a body hydrocarbon mixture manufactured by Exxon Chemical Company (USA)) is 0.6 m.
was added, and the mixture was stirred for 3 hours to react the titanium complex with the borate. Thus, containing the silica and the supernatant,
A reaction mixture having a catalytically active species formed on the silica was obtained. 20 ml of the hexane slurry of the component [D] obtained above was added thereto, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a light green solid catalyst.

(Copolymerization of ethylene and 1-butene) 800 ml of hexane was put into an autoclave having a capacity of 1.8 liters, pressurized ethylene was added to the autoclave, the internal pressure of the autoclave was increased to 1 MPa, and 5 ml of 1-butene was further added. Was placed in an autoclave. Next, the internal temperature of the autoclave was raised to 75 ° C., and the slurry of the solid catalyst obtained above was added to the autoclave in an amount such that the weight of the solid catalyst became 20 mg, and copolymerization of ethylene and 1-butene was started. did. The internal pressure of the autoclave is 1MPa
The copolymerization was carried out for 30 minutes while adding ethylene to the autoclave so as to maintain the temperature of the autoclave. After the copolymerization was completed, the reaction mixture (copolymer slurry) was extracted from the autoclave, and the catalyst was deactivated with methanol. Thereafter, the reaction mixture is filtered, washed and dried to obtain a dry powder 4 of the copolymer.
0 g was obtained. When inspecting the inside of the autoclave,
No deposit of polymer was observed on the inner wall of the autoclave or the like. The catalytic activity of the catalyst is 2340 kg-PE
/ G-Ti · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.31 g / cm ^3.
And exhibited extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0102]

Example 2 (Preparation of Component [A] and Component [D]) In the same manner as in Example 1, 50 ml of triethylaluminum-treated silica slurry was obtained as Component [A].
On the other hand, as a component [D], a hexane solution of triethylaluminum (concentration: 1M) was used in the reaction of the example in a proportion of 0.9.
A similar reaction was carried out except that the addition of the same was carried out to obtain 50 ml of a hexane slurry of the component [D] in which a part of the hydroxyl groups remained.
When the amount of hydroxyl groups in the component [D] was determined in the same manner as in Example 1, it was estimated to be 0.3 mmol per 1 g of silica.

(Preparation of Catalyst Supported on Silica) Bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) 1.1
4 g was added to and dissolved in 10 ml of toluene to obtain a 100 mM toluene solution of borate. Methylalumoxane (MMA manufactured by Tosoh Akzo Co., Ltd.) was added to this toluene solution of borate.
0.5 ml of O3A (a 1.96 mM toluene solution) was added, and toluene was further added to adjust the concentration of the borate to 50 mM in terms of borate.
And further stirred at 70 ° C. for 1 hour.
A mixed solution was obtained. Slurry 5 of component [A] obtained above
1.4 ml of the above reaction mixture containing borate in 0 ml was added and stirred for 1 hour, and the borate was supported on silica. Thus, a slurry of borate-supported silica was obtained.

To the obtained slurry, 10 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added. Solution 0.7 obtained by dissolving in 100 ml of Isopar E
Then, the mixture was stirred for 3 hours to react the titanium complex with the borate. 20 ml of the hexane slurry of the component [D] obtained above was added thereto, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a light green solid catalyst.

(Copolymerization of Ethylene and 1-Butene) Copolymerization was carried out in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 40 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no deposit of polymer was observed on the inner wall or the like of the autoclave. The catalytic activity of the catalyst is 2005kg-
PE / g-Ti · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.31 g / c.
m ³ , showing extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0106]

Example 3 (Preparation of component [A] and component [D]) In the same manner as in Example 1, component [A] and component [D] were obtained. (Preparation of catalyst supported on silica) 1.21 g of bis (hydrogenated tallowalkyl) methylammonium-tetrakis (pentafluorophenyl) borate (hereinafter abbreviated as “borate”) was added to 10 ml of toluene and dissolved, A 100 mM toluene solution of borate was obtained.

To this toluene solution of borate, 5 ml of a 0.1 M toluene solution of trimethylaluminum was added at room temperature, and toluene was further added to adjust the borate concentration in the toluene solution to 50 mM, followed by stirring at room temperature for 1 hour. A reaction mixture containing borate was obtained. 1.2 ml of this reaction mixture containing the borate was added to 50 ml of the slurry of the component [A] obtained above, and the mixture was stirred for 1 hour to carry the borate on silica. Thus, a slurry of borate-supported silica was obtained.

To the obtained slurry, 10 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added. Solution obtained by dissolving in 100 ml of Isopar E 0.6
Then, the mixture was stirred for 3 hours to react the titanium complex with the borate. 25 ml of the hexane slurry of the component [D] obtained above was added thereto, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a light green solid catalyst.

(Copolymerization of Ethylene and 1-Butene) Copolymerization was carried out in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 31 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no deposit of polymer was observed on the inner wall or the like of the autoclave. The catalytic activity of the catalyst is 1942 kg-
PE / g-Ti · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.32 g / c.
m ³ , showing extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0110]

Example 4 (Preparation of Component [A] and Component [D]) Components [A] and [D] were obtained in the same manner as in Example 1 except that triisobutylaluminum was used instead of triethylaluminum. Was. (Preparation of Catalyst Supported on Silica) 1.14 g of bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) was added to toluene 1
It was added to 0 ml and dissolved to obtain a 100 mM toluene solution of borate.

To a toluene solution of this borate was added 2.5 ml of a 0.1 M toluene solution of ethoxydiethylaluminum.
Was added at room temperature, and toluene was further added to adjust the borate concentration in the toluene solution to 50 mM, followed by stirring at room temperature for 1 hour to obtain a reaction mixture containing borate. 0.1 M toluene solution of ethoxydiethyl aluminum
2 ml were mixed with 50 m of the slurry of component [A] obtained above.
and stirred for 15 minutes to obtain a mixture.

To this mixture, 1.6 ml of the above reaction mixture containing borate was added, and the borate was supported on silica.
Thus, a slurry of borate-supported silica was obtained. 10 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) is added to 100 ml of Isopar E to the obtained slurry. 1.6 ml of the solution obtained by dissolution was added, and the mixture was stirred for 3 hours to react the titanium complex with borate. To this, 15 ml of a hexane slurry of the component [D] obtained above was added, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a light green solid catalyst.

(Copolymerization of ethylene and 1-butene) Copolymerization was carried out in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 36 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no deposit of polymer was observed on the inner wall or the like of the autoclave. The catalytic activity of the catalyst is 1466 kg-
PE / g-Ti · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.30 g / c.
m ³ , showing extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0114]

Example 5 (Preparation of component [A] and component [D]) In the same manner as in Example 1, component [A] and component [D] were obtained. (Preparation of Catalyst Supported on Silica) 1.14 g of bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) was added to toluene 1
It was added to 0 ml and dissolved to obtain a 100 mM toluene solution of borate.

To this toluene solution of borate, 10 ml of a 0.1 M toluene solution of ethoxydiethylaluminum was added at room temperature, and further toluene was added to adjust the borate concentration in the toluene solution to 50 mM.
After stirring for an hour, a reaction mixture containing borate was obtained. 1.6 ml of this reaction mixture containing borate was obtained above,
50 ml of the slurry of the component [A] was added, and the mixture was stirred for 1 hour.
The borate was supported on silica. Thus, a slurry of borate-supported silica was obtained.

To the obtained slurry, 10 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added. Solution obtained by dissolving in 100 ml of Isopar E 0.6
Then, the mixture was stirred for 3 hours to react the titanium complex with the borate. To this, 15 ml of a hexane slurry of the component [D] obtained above was added, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a light green solid catalyst.

(Copolymerization of Ethylene and 1-Butene) Copolymerization was carried out in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 32 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no deposit of polymer was observed on the inner wall or the like of the autoclave. The catalytic activity of the catalyst is 1738kg-
PE / g-Ti · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.32 g / c.
m ³ , showing extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0118]

Example 6 (Preparation of component [A] and component [D]) 1 g
Silica P-10 (manufactured by Fuji Silysia Ltd., Japan) was calcined at 500 ° C. for 6 hours in a nitrogen atmosphere to be dehydrated. The amount of surface hydroxyl groups of the dehydrated silica is 1.1 mmol / g-Si
It was O _2. 1 g of this dehydrated silica is mixed with 40 ml of hexane.
Dispersed therein to obtain a slurry. A hexane solution of triethylaluminum (concentration 1M) was added to the obtained slurry for 5 minutes.
ml and stirred for 1 hour to react triethylaluminum with the surface hydroxyl groups of the silica. The component [A] was obtained. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation, and an appropriate amount of hexane was added to disperse the triethylaluminum-treated silica in hexane. This operation was repeated five times to remove unreacted triethylaluminum in the supernatant. Thereafter, an appropriate amount of hexane was added to obtain 50 ml of a hexane slurry of silica treated with triethylaluminum. The supernatant removed by decantation was subjected to a test to determine the triethylaluminum content of the supernatant. As a result of the test, the triethylaluminum content of the supernatant was 3.7.
It turned out to be 5 mmol.

On the other hand, a similar reaction was carried out except that 0.5 ml of a hexane solution of triethylaluminum (concentration: 1 M) was added in the above reaction, to obtain 50 ml of a hexane slurry of the component [D] in which a part of hydroxyl groups remained. . Example 1
When the amount of hydroxyl groups in the component [D] was determined in the same manner as in the above, it was estimated that the amount was 0.45 mmol per 1 g of silica.

(Preparation of Catalyst Supported on Silica) Bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) 1.1
4 g was added to and dissolved in 10 ml of toluene to obtain a 100 mM toluene solution of borate. Ethanol 0.018
ml was gradually added to 3 ml of a 0.1 M toluene solution of trioctyl aluminum at 0 ° C over 30 minutes, and the resulting mixture was heated to 70 ° C and stirred at 70 ° C for 1 hour to obtain a reaction mixture. This reaction mixture was added to the above-obtained borate toluene solution at room temperature, and further toluene was added to adjust the borate concentration in the toluene solution to 50 mM, followed by stirring at room temperature for 1 hour, and the reaction mixture containing borate. I got

1.2 ml of this reaction mixture containing borate
Was added to 50 ml of the slurry of the component [A] obtained above, and the mixture was stirred for 1 hour to carry a borate on silica. Thus, a slurry of borate-supported silica was obtained. [(Nt-butylamide)] was added to the obtained slurry.
(Tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter, referred to as
0.6 mmol of a solution obtained by dissolving 10 mmol of “titanium complex” in 100 ml of Isopar E was added, and the mixture was stirred for 3 hours to react the titanium complex with borate. 20 ml of the hexane slurry of the component [D] obtained above was added thereto, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a light green solid catalyst.

(Copolymerization of Ethylene and 1-Butene) Copolymerization was conducted in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 38 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no deposit of polymer was observed on the inner wall or the like of the autoclave. The catalytic activity of the catalyst is 1852 kg-
PE / g-Ti · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.32 g / c.
m ³ , showing extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0123]

Example 7 (Preparation of component [D]) A component [D] was obtained in the same manner as in Example 1. (Preparation of catalyst supported on silica) 1 g of silica [manufactured by Fuji Silysia Ltd. (Japan); pore volume 1.10 cm ³ /
g, specific surface area is 318 m ² / g, bulk density is 0.38 g / c
m ³ ] was fired at 150 ° C. for 6 hours under a nitrogen atmosphere, and dehydrated. The amount of surface hydroxyl groups of the dehydrated silica is 2.1 mmol
/ G-SiO ₂ . 1 g of this dehydrated silica was dispersed in 40 ml of toluene to obtain a slurry. To the obtained slurry, a toluene solution of methylaluminoxane (MMAO3A manufactured by Tosoh Akzo, 1.96 mM toluene solution)
5 ml was added dropwise over 15 minutes under a nitrogen atmosphere while maintaining the temperature of the suspension at -5 ° C. Thereafter, methylaluminoxane reacts with the surface hydroxyl group of the silica under a nitrogen atmosphere for 1 hour at 0 ° C., 1 hour at room temperature, and further reflux for 3 hours, and the silica treated with the methylaluminoxane and the supernatant are reacted. A component [A] was obtained in which all surface hydroxyl groups of the silica treated with methylaluminoxane were crushed.

Thereafter, the mixture was cooled to 20 ° C., and the supernatant in the obtained reaction mixture was removed by decantation.
By adding an appropriate amount of toluene, the silica treated with methylaluminoxane was dispersed in toluene. This operation was repeated five times to remove unreacted methylaluminoxane in the supernatant. Thereafter, an appropriate amount of toluene was added to obtain 50 ml of a toluene slurry of silica treated with methylaluminoxane. The supernatant removed by decantation was subjected to a test to determine the methylaluminoxane content of the supernatant. As a result of the test, it was found that the methylaluminoxane content of the supernatant was 1.52 mmol.

The resulting slurry was mixed with bis (n-butylcyclopentadienyl) zirconium dichloride (hereinafter referred to as “bis (n-butylcyclopentadienyl) zirconium dichloride”).
1 mmol of toluene (called “zirconium complex”)
2 ml of a solution obtained by dissolving in 00 ml was added, and the mixture was stirred at room temperature for 3 hours to react the zirconium complex with methylaluminoxane. After completion of the reaction, decantation with hexane was performed five times to obtain 50 ml of a hexane slurry. 20 ml of the hexane slurry of the component [D] obtained above was added thereto, and the mixture was stirred for 10 minutes to obtain a hexane slurry of a pale yellow solid catalyst.

(Copolymerization of Ethylene and 1-Butene) Copolymerization was carried out in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 32 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, no deposit of polymer was observed on the inner wall or the like of the autoclave. The catalytic activity of the catalyst is 3453 kg-
PE / g-Zr · hr. The resulting copolymer powder has an average particle size of 300 μm and a bulk density of 0.29 g / c.
m ³ , showing extremely excellent fluidity. Thus, it was found that the obtained copolymer powder exhibited extremely excellent powder properties.

[0127]

Comparative Example 1 (Preparation of Catalyst Supported on Silica) A hexane slurry of a light green solid catalyst was obtained in the same manner as in Example 1, except that the component [D] was not used. In this case, a slight yellow coloring was observed in the supernatant of the slurry.

(Copolymerization of Ethylene and 1-Butene) Copolymerization was carried out in the same manner as in Example 1. After the copolymerization, the reaction mixture (copolymer slurry) is removed from the autoclave.
And the catalyst was deactivated with methanol. afterwards,
The reaction mixture was filtered, washed and dried to obtain 45 g of a dry powder of the copolymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall and the like of the autoclave. The catalytic activity of the catalyst is 1880 kg-PE / g-
Ti · hr. The obtained copolymer powder had an average particle diameter of 300 μm and exhibited extremely excellent fluidity. However, the bulk density was as low as 0.24 g / cm ³ .

[0129]

Example 8 (Preparation of a catalyst supported on silica) The same catalyst as in Example 1 was produced in the same manner as in Example 1 except that the amount used was increased without changing the amount ratio of the raw materials. A slurry containing 2 kg was obtained. (Copolymerization of ethylene and 1-hexene) In the presence of the solid catalyst obtained in the form of a slurry, continuous copolymerization of ethylene and 1-hexene was carried out for about 7 days in a pilot plant. This continuous copolymerization reaction was performed under the following conditions. The internal pressure of the reactor was maintained at 1 MPa by feeding ethylene. The reaction temperature was 75 ° C. The speed of copolymerization was maintained at 10 kg / hr. In addition, 1-hexene was continuously supplied so that the density of the copolymer became 0.94 g / cm ³ . Further, the MFR of the copolymer was adjusted so that the MI value was 2 by continuously supplying hydrogen gas.

After the completion of the continuous copolymerization reaction for about 7 days, the reactor was opened and the inside thereof was examined. As a result, no deposit of polymer was observed on the inner wall of the reactor. The catalytic activity of the catalyst was 1870 kg-PE / g-Ti · hr. The resulting powder of the copolymer has a bulk density of 0.38 g / cm.
^{It had} a height of ³ and an average particle size of about 250 μm, and had sufficient fluidity for practical use.

[0131]

Comparative Example 2 (Preparation of Catalyst Supported on Silica) A hexane slurry of a light green solid catalyst equivalent to 1.4 kg was obtained in the same manner as in Example 8 except that the component [D] was not used. In this case, a slight yellow coloration was observed in the supernatant of the slurry. A slurry was obtained.

(Copolymerization of ethylene and 1-hexene) Except for adding 1 mM of triethylaluminum in hexane at a concentration of 0.05 mmol / l in the reactor, the presence of this catalyst was determined in the same manner as in Example 8. A continuous copolymerization of ethylene and 1-hexene is carried out to obtain ethylene and 1-hexene.
-A copolymer with hexene was obtained. The catalytic activity of the catalyst is 3
It was 500 kg-PE / g-Ti · hr. After the end of the continuous copolymerization, the reactor was opened and the inside was examined. As a result, a deposit of polymer was observed on the inner wall of the reactor. The resulting copolymer powder had an average particle size of about 200 μm and a bulk density of 0.23 g / cm ³ .

[0133]

The catalyst for olefin polymerization of the present invention can be applied to suspension polymerization (slurry polymerization) or gas-phase polymerization of olefin, and does not cause a phenomenon such as adhesion to a reactor during polymerization. It is intended to provide an olefin polymerization catalyst, particularly an ethylene polymerization catalyst, which can produce a polymer powder having excellent powder properties with high activity, effectively and efficiently, and which can realize continuous operation of a commercial plant. is there.

Continued on the front page F-term (reference) 4J028 AA01A AB00A AB01A AC01A AC02A AC10A AC20A AC28A AC45A AC48A BA00A BA00B BA01A BA01B BA02A BB00A BB00B BB01A BB01B BB02A BC13A BC13B BC15B CA28 CA03B02 CA25B02 CA24B02 CA24B02A EB07 EB08 EB09 EB10 EB13 EB16 EB17 EB21 EC01 EC02 4J128 AA01 AB00 AB01 AC01 AC02 AC10 AC20 AC28 AC45 AC48 AD00 BA00A BA00B BA01A BA01B BA02A BB00A BB00B BB01A BB01B BB02ABC13BCA28 BC15A BC15A BC15A EB04 EB05 EB07 EB08 EB09 EB10 EB13 EB16 EB17 EB21 EC01 EC02

Claims (7)

[Claims] 1. A catalyst which reacts with [A] a solid component having substantially no hydroxyl group, [B] a soluble transition metal compound selected from Groups 3 to 11 of the periodic table, and [C] a transition metal compound [B]. A solid catalyst for olefin polymerization, comprising: an activator compound capable of forming a metal complex having activity; and [D] a solid component having substantially a hydroxyl group. 2. A solid component [D] having substantially hydroxyl groups.
Is selected from the group consisting of silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide, thorium oxide, and mixtures or composite oxides thereof. The olefin polymerization catalyst according to claim 1, wherein the catalyst is at least one substance. 3. A solid component [D] having substantially hydroxyl groups.
Is 0.05 to 10 mm / g by subjecting the solid component described in claim 2 to heat treatment at 150 ° C. or higher.
ol having hydroxyl groups on its surface, and further treating the solid component with an organometallic compound having a molar amount of 0.01 times or more and less than 1 time the molar amount of the hydroxyl groups present on the surface of the solid component. Characterized by being obtained by
The olefin polymerization catalyst according to claim 1. 4. The method according to claim 1, wherein the soluble transition metal compound [B] selected from Groups 3 to 11 of the periodic table is represented by the following formula (1). Olefin polymerization catalyst. LjWkMXpX'q (1) (wherein, L independently comprises a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group Represents an η-binding cyclic anion ligand selected from the group;
Having up to 8 substituents, each of which independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and 1 to 12 carbon atoms.
A halogen-substituted hydrocarbon group, 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, a hydrocarbylphosphino group having 1 to 12 carbon atoms, silyl A substituent having up to 20 non-hydrogen atoms selected from the group consisting of a group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms and a halosilyl group, and M represents a formal oxidation number of +2, +3 or +4 Periodic Table No. 4
A transition metal selected from the group of transition metals belonging to the group
Represents a transition metal bonded to at least one ligand L by η ⁵ , W is a divalent substituent having up to 50 non-hydrogen atoms, and L and M are each monovalent. 2 which binds at a valency, thereby cooperating with L and M to form a metallocycle
X independently represents a monovalent anionic σ-binding ligand, a divalent anionic σ-binding ligand which binds divalently with M, and L and M Selected from the group consisting of divalent anionic σ-binding ligands, each of which binds with a valence of one.
X 'independently represents a neutral Lewis base coordinating compound having up to 40 non-hydrogen atoms; X' represents an anionic sigma-bonded ligand having up to 60 non-hydrogen atoms; Is 1 or 2, provided that when j is 2, optionally two ligands L are linked to each other via a divalent group having up to 20 non-hydrogen atoms, Is a hydrocarbadiyl group having 1 to 20 carbon atoms, and a group having 1 to 12 carbon atoms.
A halohydrocarbadiyl group, a C1-12 hydrocarbyleneoxy group, a C1-12 hydrocarbyleneamino group, a silanediyl group, a group selected from the group consisting of a halosilanediyl group and a silyleneamino group, k is 0 or 1, p is 0, 1 or 2, provided that X is a monovalent anionic σ-binding ligand or a divalent anionic σ bonded to L and M P is an integer smaller than the formal oxidation number of M by 1 or more when it is a bond ligand, and p is a divalent anionic σ bond ligand where X is bonded only to M. Is an integer smaller than the formal oxidation number of M by (j + 1) or more, and q is 0, 1 or 2.) 5. An activator compound [C] capable of forming a metal complex having catalytic activity by reacting with a transition metal compound [B] is represented by the following formula (2): The catalyst for olefin polymerization according to any one of claims 1 to 4, wherein ^{[L-H] d + [} MmQp] d - (2) ( wherein represents the [L-H] d ⁺ proton donating Bronsted acid, where, L represents a neutral Lewis base, d
Is an integer of 1 to 7; [Mm ⁺ Qp] d ^- represents a compatible non-coordinating anion, wherein M is a metal or metalloid belonging to any of Groups 5 to 15 of the periodic table Wherein Q is independently hydride, halide, dihydrocarbylamide group having 2 to 20 carbon atoms, 1 to 30 carbon atoms.
Is selected from the group consisting of a hydrocarbyloxy group, a hydrocarbon group having 1 to 30 carbon atoms, and a substituted hydrocarbon group having 1 to 40 carbon atoms, provided that the number of halide Q is 1 or less, and m Is an integer from 1 to 7, p is an integer from 2 to 14, d is as defined above, and pm = d. ) 6. The catalyst component reacts with a solid component [A] having substantially no hydroxyl group, a soluble transition metal compound [B] selected from Groups 3 to 11 of the periodic table, and a transition metal compound [B] to increase the catalytic activity. A mixture obtained by previously contacting an activator compound [C] capable of forming a metal complex having the same with an equivalent amount of a solid component [D] substantially having a hydroxyl group, and using the mixture. The olefin polymerization catalyst according to any one of claims 1 to 5, wherein 7. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to any one of claims 1 to 6.