JPH09272713A - Olefin polymerization catalyst and method for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which can give a spherical olefin polymer having excellent particle properties in high polymerization activity by prepolymerizing an olefin over a catalyst component comprising a specified transition metal compound and a specified promoter and supported by a microparticulate support. SOLUTION: This catalyst is prepared by prepolymerizing an olefin over a catalyst component comprising a microparticulate support, a compound containing a group 8-10 transition metal in the periodic table and represented by formula I, at least one compound selected from among organoaluminumoxy compounds, alkylboric acid derivatives and Lewis acids and ionic compounds and optionally an organometallic compound. In formula I, M is a group 8-10 transition metal atom in the periodic table; X<1> and X<2> are each nitrogen or phosphorus; R<1> and R<2> are each hydrogen or a hydrocarbon group; m and n are each 1 or 2; R<3> is a group represented by formula II (R<6> , R<7> and R<61> to R<72> are each hydrogen or a hydrocarbon group); and R<4> and R<5> are each hydrogen, a hydrocarbon group or the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for polymerizing olefins using this catalyst, and more specifically, it can be applied to a suspension polymerization method or a gas phase polymerization method, and has a high polymerization rate. The present invention relates to an olefin polymerization catalyst capable of producing an olefin polymer which is active and has excellent particle properties, and an olefin polymerization method using this catalyst.

[0002]

2. Description of the Related Art Conventionally, as a catalyst for producing an α-olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound, and a vanadium compound have been used. A vanadium-based catalyst composed of an organoaluminum compound is known.

A Ziegler catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

Recently, as a new olefin polymerization catalyst, an olefin polymerization catalyst comprising a nickel compound or a palladium compound and a cocatalyst such as an aluminoxane or an ionic compound has been proposed (J. Am. Chem. Soc. 1995, 1
17,6414-6415).

The catalyst composed of the nickel compound or the palladium compound and the cocatalyst as described above is mostly soluble in the reaction system, and in most cases, the production process is limited to the solution polymerization system, and the polymer having a high molecular weight is used. When a polymer-containing solution is produced, the viscosity of the solution containing the polymer becomes extremely high and the productivity lowers, and the bulk specific gravity of the polymer obtained after the post-treatment of polymerization is small, and spherical olefins having excellent particle properties are obtained. There is a problem that it is difficult to produce a polymer.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and can be applied to a suspension polymerization method or a gas phase polymerization method, and has high polymerization activity and excellent particle properties. Another object of the present invention is to provide a catalyst for olefin polymerization which can produce a spherical olefin polymer and which gives a copolymer having a narrow composition distribution when two or more kinds of monomers are copolymerized.

Another object of the present invention is to provide a method for polymerizing olefins using a catalyst having such good properties.

[0008]

SUMMARY OF THE INVENTION An olefin polymerization catalyst according to the present invention comprises: (A) a particulate carrier; (B) a transition metal compound of Groups 8 to 10 of the periodic table represented by the following general formula (I): C) At least one compound selected from (C-1) organoaluminum oxy compound, (C-2) alkylboronic acid derivative and (C-3) Lewis acid or ionic compound, and optionally (D) It is characterized in that an olefin is prepolymerized with a catalyst component composed of an organometallic compound.

[0009]

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(In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R 1
¹ and R ² may be the same or different from each other,
Represents a hydrogen atom or a hydrocarbon group, m and n may be the same or different from each other, and 1 or 2,
R is a number satisfying the valences of X ¹ and X ² , respectively, and R
³ is

[0011]

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(However, R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹
And R ^{72, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. ), R ⁴ and R ^{5, which} may be the same or different, are each a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR ⁹ ,
-N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ (provided that, R ⁸ ~
R ¹¹ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ^{10 s} or R ^{11 s} may be linked to each other to form a ring. )
And R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ ,
Two or more of R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may be linked to each other to form a ring. In the present invention, the transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula (I ′).

[0013]

[Chemical 6]

(In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R 1
¹ and R ² may be the same or different from each other,
A hydrogen atom or a hydrocarbon group, R ⁶ and R ⁷ are
They may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, and R ⁴ and R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR. ^9, -N (R ¹⁰⁾ ₂ or -P
(R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ^{10 s} or R ^{11 s} are linked to each other to form a ring. R ⁴ and R ^4
5 may combine with each other to form a ring, and R ¹ , R
^Two or more of ² , R ⁶ and R ⁷ may be linked to each other to form a ring. The olefin polymerization catalyst of the present invention can be applied to a suspension polymerization method or a gas phase polymerization method, and can produce a spherical olefin polymer having a high polymerization activity and excellent particle properties, and two kinds. When the above monomers are copolymerized, a copolymer having a narrow composition distribution is obtained.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the above-mentioned catalyst.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst according to the present invention and the olefin polymerization method using the catalyst will be specifically described below.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises (A) a particulate carrier, (B) a transition metal compound of Groups 8 to 10 of the periodic table, (C) an organoaluminum oxy compound, Preliminary polymerization of olefin on a catalyst component consisting of at least one compound selected from C-2) alkylboronic acid derivative and (C-3) Lewis acid or ionic compound, and optionally (D) organometallic compound Is formed.

First, the catalyst for olefin polymerization of the present invention is formed.
Each catalyst component formed will be described.(A) Fine particle carrier The (A) particulate carrier used in the present invention is an inorganic or
Is an organic compound having a particle size of 10 to 300 μm,
It is preferably in the form of granules or fine particles of 20 to 200 μm.
Solids are used. Of these, the inorganic compound is porous
Oxide is preferred, specifically SiO_Two, Al_TwoO_Three, M
gO, ZrO, TiO_Two, B_TwoO_Three, CaO, ZnO,
BaO, ThO_TwoOr a mixture of these, even
If SiO _Two-MgO, SiO_Two-Al_Two O_Three, SiO_Two-Ti
O_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-T
iO_Two-MgO etc. can be illustrated. Among these
With SiO_TwoAnd Al_Two O_ThreeA few selected from the group consisting of
It is preferable to use at least one component as a main component.

The inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, L
It may contain carbonate, sulfate, nitrate and oxide components such as i ₂ O.

The properties of the (A) particulate carrier vary depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g.
It is preferably in the range of 100 to 700 m ² / g, and the pore volume is preferably in the range of 0.3 to 2.5 cm ³ / g. The carrier may be 100 to 1000 ° C. if necessary,
Preferably, it is used by firing at 150 to 700 ° C.

In such a particulate carrier (A), it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably It is desirable that the content is 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the particulate carrier (A) are determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss after drying for a period of time is determined and shown as a percentage with respect to the weight of the carrier before drying. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Surface hydroxyl group content (wt%) = {(X−Y) / X} × 100 Further, the fine particle carrier (A) that can be used in the present invention has a particle size in the range of 10 to 300 μm. Examples thereof include granular or particulate solids of organic compounds. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene and other (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms or vinylcyclohexane, A polymer or copolymer formed mainly with styrene can be exemplified.

(B) Transition metal compound of Group 8 to 10 of the periodic table The transition metal compound of Group 8 to 10 of the periodic table (B) used in the present invention is a transition metal represented by the following general formula (I). It is a compound.

[0026]

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In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, preferably nickel, palladium or platinum. X ¹ and X ² may be the same or different from each other and represent a nitrogen atom or a phosphorus atom.

R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
sec-Butyl group, tert-butyl group, pentyl group, hexyl group, etc., linear or branched alkyl group having 1 to 20 carbon atoms; phenyl group, naphthyl group, etc., having 6 to 20 carbon atoms Group; these aryl groups have 1 to 5 substituents such as an alkyl group having 1 to 20 carbon atoms.
Examples thereof include a substituted aryl group substituted with an individual.

M and n, which may be the same or different, are 1 or 2 and are numbers satisfying the valences of X ¹ and X ² , respectively. R ³ is

[0030]

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Is shown. However, R ⁶ , R ⁷ , R ⁶¹ ,
R ⁶² , R ⁷¹ and R ^{72, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group similar to R ¹ and R ² .

The above R ¹ , R ² , R ⁶ (or R ⁶¹ ,
R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may form a ring by connecting two or more of them, preferably adjacent groups, to each other.

R ⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include alkyl groups having 1 to 20 carbon atoms similar to R ¹ and R ² and aryl groups having 6 to 20 carbon atoms, benzyl groups and the like. 7 to 20 aralkyl groups and the like can be mentioned. One or more substituents such as the alkyl group having 1 to 20 carbon atoms may be substituted on the aryl group and the aralkyl group.

Further, as R ⁴ and R ⁵ , -OR ⁸ ,
-SR ^9, a group represented by -N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ is also shown. R ^{8 to} R ¹¹ are the same as R ¹ and R ² described above.
Similarly, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms such as a cyclohexyl group, and a carbon number 7 to 7 such as a benzyl group. 20 aralkyl groups; organic silyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group and triethylsilyl group. The aryl group and the aralkyl group may be substituted with one or more substituents such as the alkyl group having 1 to 20 carbon atoms. And R
^10's or R ^11's may be linked to each other to form a ring.

R ⁴ and R ⁵ may be linked to each other to form a ring. The transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula (I ′).

[0037]

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(Wherein M, X ¹ , X ² , R ¹ , R ² , R
⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in the general formula (I). ) Specific examples of the transition metal compound represented by the general formula (I ′) include the following compounds.
In the following formula, iPr represents an isopropyl group.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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In addition to the above, examples of the transition metal compound represented by the general formula (I ') include compounds in which palladium or nickel in the above compounds is replaced by platinum.

The compounds represented by the general formula (I) include the following compounds in addition to the above. In the following formula, iPr represents an isopropyl group.

[0051]

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[0052]

[Chemical 21]

In addition to the above, examples of the transition metal compound represented by the general formula (I) include compounds in which palladium or nickel in the above compounds is replaced by platinum.

The above transition metal compounds may be used alone or in combination of two or more. (C-1) Organoaluminum Oxy Compound The (C-1) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method and is usually obtained as a solution of 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 cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (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 aluminoxane may contain a small amount of organometallic component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n-.
Butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., trialkylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, etc. Dialkylaluminum halides such as tricycloalkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dimethylaluminum methoxide, diethylaluminum ethoxy And dialkylaluminum aryloxides such as diethylaluminum alkoxide and diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as an organoaluminum compound used for preparing aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

[0059] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... (II) ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used alone or in combination of two or more.

As the solvent used for the preparation of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Yes, it is insoluble or sparingly soluble in benzene.

The above (C-1) organoaluminum oxy compounds may be used alone or in combination of two or more. (C-2) Alkylboronic Acid Derivative Examples of the alkylboronic acid derivative (C-2) used in the present invention include compounds represented by the following general formula (III).

[0063]

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In the formula, R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms. R < ¹³ >, which may be the same or different, each represents a hydrogen atom, a halogen atom, a siloxy group, a lower alkyl group-substituted siloxy group or a hydrocarbon group having 1 to 10 carbon atoms.

The alkylboronic acid derivative (B-2) represented by the general formula (III) includes an alkylboronic acid represented by the following general formula (IV) and R ¹² -B- (OH) ₂ (IV) (In the formula, R ¹² represents the same group as described above.) Reacting with an organoaluminum compound in an inert solvent in an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours. Can be manufactured by

Specific examples of the alkylboronic acid represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n. -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

The organoaluminum compound to be reacted with the alkylboronic acid is represented by the following general formula (V-
Examples thereof include organoaluminum compounds represented by 1), (V-2) and (V-3).

(R ¹³ ) _3-p- Al-Y _p (V-1) (R ¹³ ) _3-p- Al- [OSi (R ¹⁴ ) ₃ ] _p (V-2) (R ¹³ ) _{2 -Al-O-Al- (R} 13) 2 ... (V-3) ( in the formula, Y is a hydrogen atom or a halogen atom, R ¹⁴ is
A hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms, p is 0 ≦ p <3, and R ¹³ is the same group as described above. ) Specific examples of the organoaluminum compounds represented by the general formulas (V-1), (V-2) and (V-3) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n. -Butyl aluminum, triisobutyl aluminum, tri
sec-Butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum and other trialkyl aluminum, tricyclohexyl aluminum, tricyclooctyl aluminum and other tricycloalkyl aluminum, dimethyl aluminum chloride Dialkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, diethyl Examples thereof include dialkylaluminum aryloxides such as aluminum phenoxide.

Of these, trialkylaluminums and tricycloalkylaluminums are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The above-mentioned (C-2) alkylboronic acid derivative may be used alone or in combination of two or more kinds. (C-3) Lewis acid or ionic compound Lewis acid or ionic compound (B-
3), JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, and JP-A-3-207.
703, JP-A-3-207704, US-
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent No. 547718.

Specifically, as the Lewis acid, BR is
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group, a trifluoromethyl group or fluorine), and examples thereof include trifluoroboron, triphenylboron, Tris (4-fluorophenyl) boron, Tris (3,5-difluorophenyl) boron, Tris (4-fluoromethylphenyl) boron, Tris (pentafluorophenyl) boron, Tris (p-tolyl) boron, Tris (o- Trily) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (VI).

[0073]

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In the formula, R ¹⁵ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{16 to} R ^{19, which} may be the same or different, are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri (n-butyl) ammonium cation; N, N-diethylaniline. Nium cation, N,
N, N- such as N-2,4,6-pentamethylanilinium cation
Dialkylanilinium cation; di (isopropyl)
Examples thereof include dialkylammonium cations such as ammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation.

R ¹⁵ is preferably a carbonium cation, an ammonium cation or the like, particularly preferably a triphenylcarbonium cation or an N, N-diethylanilinium cation.

The ionic compound is represented by the following formula (VII)
Boron compounds represented by are preferred.

[0080]

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(In the formula, Et represents an ethyl group.) Further, examples of the ionic compound include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt. You can also

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and trimethylammonium tetra (p). -Tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, Examples include 4,6-pentamethylanilinium tetra (phenyl) boron.

Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
Examples also include N, N-diethylanilinium pentaphenylcyclopentadienyl complex and a boron compound represented by the following formula (VIII).

[0086]

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Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate and bis [tri (n-butyl) ammonium]. ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodeca hydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,
7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarbaundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodeca hydride-8-
Methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salts of anions such as; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (N-Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarbaundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Examples thereof include salts of metal carborane anions such as carbaundecaborate) nickelate (IV).

The (C-3) Lewis acid or ionic compound as described above may be used alone or in combination of two or more. (D) Organometallic compound As the (D) organometallic compound used as necessary in the present invention, specifically, the following organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table are used. To be

[0090] (D-1) In the general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X is a halogen atom, and m is 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3, and m + n + p + q = 3. The organoaluminum compound represented by).

(D-2) General formula M ¹ AlR ^a ₄ (In the formula, M ¹ represents Li, Na and K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a Group 1 metal and aluminum.

(D-3) Formula R ^a R ^b M ² (wherein R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). A dialkyl compound of a Group 2 or Group 12 metal, which represents a hydrocarbon group and M ² is Mg, Zn, or Cd).

Examples of the organoaluminum compound belonging to the above (D-1) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by), the general formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, Preferably, it represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, q is a number 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

Specific examples of the aluminum compound belonging to (D-1) include tri-n-alkylaluminum such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-aluminum. -Butyl aluminum, tri 2-methylbutyl aluminum, tri 3-
Methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4-
Methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri
Tri-branched alkyl aluminum such as 2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triisoprenyl aluminum and the like Trialkenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; parts having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 Alkyloxylated aluminum; Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Diethyl aluminum hydride;
Dialkyl aluminum hydrides such as dibutyl aluminum hydride; Other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride, alkyl aluminum dihydrides such as propyl aluminum dihydride; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy Mention may be made of partially alkoxylated and halogenated alkylaluminum such as bromide.

A compound similar to (D-1) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of the compound belonging to (D-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

[0097] Besides, as the organic metal compound (D), the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are positive numbers And z ≧ 2x), it is also possible to use isoprenylaluminum.

In addition to the above, the organometallic compound (D)
As, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, It is also possible to use diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like.

It is also possible to use a compound capable of forming the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium.

As the organometallic compound (D) used in the present invention, a metal compound having a branched alkyl group is preferable, and a metal compound having an isobutyl group is particularly preferable, and a triisobutyl metal compound is particularly preferable. Aluminum is preferable as the metal, and triisobutylaluminum is most preferable.

The organometallic compound (D) acts as an alkylating agent, and R bonded to the transition metal (M) in the transition metal compound (B) represented by the general formula (I).
^{When 4} and / or R ⁵ is an atom or group other than an alkyl group, for example, a halogen atom such as chlorine or bromine; a group such as an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group, these are substituted with an alkyl group. To do. Such an alkyl group-substituted transition metal compound (B) is (C)
Reacts with components, especially component (C-3) to form ionic complexes with high catalytic activity.

The (D) organometallic compound is a scavenger.
It also acts as a jar and removes water and other impurities from the system.
Since the reaction system is removed to keep the system clean, the catalyst activity is stable and highly active.
The effect of being able to express is obtained. this
Action binds to transition metal (M) in transition metal compound (B)
Doing R^FourAnd / or R^FiveIs an alkyl group
Is also expressed. Therefore, the organometallic compound (D) is
Transition gold in transition metal compound (B) represented by general formula (I)
R bound to genus (M)^FourAnd / or R ^FiveIs al
When used together with a transition metal compound (B) which is a kill group
Also, the same effect as described above can be obtained.

The (D) organometallic compound as described above is 1
These are used alone or in combination of two or more. Olefin polymerization catalyst (preliminary polymerization catalyst) used in the present invention
Is the fine particle carrier (A), the transition metal compound (B),
(C-1) at least one compound (C) selected from organoaluminum oxy compound, (C-2) alkylboronic acid derivative and (C-3) Lewis acid or ionic compound, and optionally an organometallic compound It can be prepared by introducing an olefin into an inert hydrocarbon solvent in the presence of (D) and performing prepolymerization.

FIG. 1 shows an example of the process for preparing the olefin polymerization catalyst according to the present invention. The olefin used in the prepolymerization is an α-olefin having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- Examples include octene, 1-decene, 1-dodecene, 1-tetradecene and the like.

Further, as the monomer used in the prepolymerization, a polar monomer can be mentioned. Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,2) 1) -5
Α, β-unsaturated carboxylic acids such as heptene-2,3-dicarboxylic acid, and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium and calcium; methyl acrylate, ethyl acrylate, n-propyl acrylate. , Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate. Α, β-unsaturated carboxylic acid esters such as isobutyl methacrylate; unsaturated dicarboxylic acids such as maleic acid and itaconic acid;
Vinyl acetate, vinyl propionate, vinyl caproate,
Vinyl esters such as vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate;
Examples thereof include unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and itaconic acid monoglycidyl ester.

Of these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable. Specific examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof.

In the prepolymerization, the component (B) is usually 10 ^-6 to 10 in terms of the transition metal atom in the component (B).
2 × 10 ^-2 mol / liter (solvent), preferably 5 × 1
Used in an amount of 0 ^-5 to 10 ^-2 mol / liter (solvent),
The component (B) is usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 1 in terms of transition metal atom per 1 g of the component (A).
It is used in an amount of 0 ^{−5 to} 2 × 10 ⁻⁴ mol.

The component (C-1) and the component (C-2) are the components (C-
1) Or the molar ratio of the aluminum atom in the component (C-2) to the component (B) [(C-1) / (B) or (C-2) /
(B)] is usually 10 to 1000, preferably 20 to 5
It is used in an amount such that it becomes 00.

The component (C-3) has a molar ratio [(C-3) / (B)] of the component (C-3) and the component (B) of usually 1 to 10, preferably 1 to 5. Used in such an amount that The component (D) used as necessary has a molar ratio [(D) / (B)] of the component (D) and the component (B) of usually 0.01 to 100, preferably 0.05 to 50. Used in such an amount that

The prepolymerization temperature is -20 to 70 ° C, preferably -10 to 60 ° C, and the prepolymerization time is 0.5 to
It is 100 hours, preferably about 1 to 50 hours. Olefin polymerization catalyst (preliminary polymerization catalyst) used in the present invention
Means the components (A) to (C), and optionally the component (D).
It can be prepared by introducing an olefin into an inert hydrocarbon solvent and preliminarily polymerizing it in the presence of a component (A), (B), (C) and the olefin, and (D) if necessary. The contact order of is selected arbitrarily. In particular,
For example, it is prepared as follows.

(1) The component (A) is suspended in an inert hydrocarbon. Next, the component (B) and the component (C) are added to this suspension, and a method of introducing an olefin into the suspension (2) The component (A) is suspended with an inert hydrocarbon. Next, the component (B) and the component (C) are added to this suspension and reacted for a predetermined time, and then the supernatant liquid is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to the inert hydrocarbon containing the component (D), and the olefin is introduced therein (3) The component (A) is suspended in the inert hydrocarbon. To do. Then, the component (C) is added to this suspension, and the mixture is reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. Method of adding component (B) into this system and introducing olefin into the system (4) Component (A) is suspended in inert hydrocarbon. Then, the component (C) is added to this suspension, and the mixture is reacted for a predetermined time. The supernatant is then removed and the solid component obtained is resuspended with an inert hydrocarbon containing component (D). Method of adding component (B) into this system and introducing olefin into the system (5) Component (A) is suspended with an inert hydrocarbon. Then, the component (C) is added to this suspension, and the mixture is reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. The component (B) is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Then, the solid catalyst component obtained above is added to the inert hydrocarbon containing the component (D), and the olefin is introduced therein.

(6) The component (A) is suspended in an inert hydrocarbon. Next, the component (B) is added to this suspension, and the mixture is reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. A method of adding the component (C) into the system and introducing the olefin into the system.

(7) The component (A) is suspended in an inert hydrocarbon. Next, the component (B) is added to this suspension, and the mixture is reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. The component (C) is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Then, the solid catalyst component obtained above is added to the inert hydrocarbon containing the component (D), and the olefin is introduced therein.

(8) The above-mentioned methods (1) to (7), wherein the component (A) is previously treated with a halogen-containing silicon compound, an organoaluminum compound or the like. The olefin (co) polymer produced by the prepolymerization carried out as described above is 0.1 to 100 per 1 g of the component (A).
g, preferably 0.2 to 50 g, more preferably 0.3
It is desirable that the amount is ˜30 g. Further, in the prepolymerization catalyst, the component (B) as a transition metal atom is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ g atom, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ g per 1 g of the component (A). Supported in atomic quantities, components
(C-1) or (C-2) is the aluminum atom (Al) in the component (C-1) or (C-2) and the molar ratio ((M)) to the transition metal atom (M) in the component (B). Al / M), 5 to 50
The component (C-3) is supported in an amount of 0, preferably in the range of 10 to 300, and the component (C-3) has a molar ratio ((C-3) / M) to the transition metal atom (M) in the component (B) of 0. It is desirable that the carrier be loaded in an amount of 0.4 to 8, preferably 0.5 to 5.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Although a molecular weight modifier such as hydrogen may be used, even when such a molecular weight modifier is used, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.2 to 7 dl /
It is desirable to produce a prepolymer such that it is in the g range, preferably 0.5 to 5 dl / g.

In the present invention, the polymerization or copolymerization of the olefin is carried out in the presence of the prepolymerization catalyst as described above or in the presence of the prepolymerization catalyst (component) as described above and the organometallic compound (D). , In the gas phase or in the liquid phase in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene;
Examples include petroleum fractions such as gasoline, kerosene, and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

When carrying out the slurry polymerization method or the gas phase polymerization method, the above-mentioned prepolymerization catalyst usually has a concentration of the transition metal atom in the prepolymerization catalyst of 10 ⁻⁸ to It is desirable to use an amount of 10 ⁻³ gram atom / liter, preferably 10 ⁻⁷ to 10 ⁻³ gram atom / liter.

Further, in the polymerization, in addition to the component (C) supported on the particulate carrier (A), the component (C) not supported may be used. Further, the component (D) may be used in the polymerization.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C, and when carrying out the gas phase polymerization method. The polymerization temperature is usually 0 to 120 ° C., preferably 20.
Is in the range of -100 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. In the present invention, the olefin polymerization catalyst can contain other components useful for olefin polymerization in addition to the above-mentioned components.

As the olefin which can be polymerized by the olefin polymerization catalyst of the present invention, an α-olefin having 2 to 20 carbon atoms, for example, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; Cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4 , 4a, 5,8,8a-
Examples thereof include octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0124] Examples of the monomer that can be polymerized with the olefin polymerization catalyst include polar monomers. Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo ( Α, β-unsaturated carboxylic acids such as 2,2,1) -5-heptene-2,3-dicarboxylic acid and their metal salts such as sodium, potassium, lithium, zinc, magnesium and calcium; methyl acrylate; Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,
Α, β- such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, etc.
Unsaturated carboxylic acid esters; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. And unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid.

[0125]

The olefin polymerization catalyst according to the present invention is
When polymerized by a slurry polymerization method or a gas phase polymerization method of an olefin, the polymer is not attached to the reactor and the particle properties are excellent, and when applied to the copolymerization of two or more olefins, the molecular weight distribution and composition distribution are A narrow olefin copolymer is obtained.

[0126]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0127]

[Example 1] [Preparation of prepolymerization catalyst] 400 ml that was sufficiently replaced with nitrogen
5g of silica dried in a flask at 250 ° C for 10 hours
Was suspended in 100 ml of toluene and then cooled to 0 ° C. Then, 28 ml of a toluene solution of methylaluminoxane (Al; 1.33 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Continue to react at 0 ° C for 30 minutes, then 95 hours over 95 hours
The temperature was raised to 0 ° C., and the reaction was performed at that temperature for 20 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method.

The solid component thus obtained was washed twice with toluene and twice with hexane, and then hexane 1 containing 0.05 mmol of triisobutylaluminum was added.
Resuspend in 00 ml. After 0.3 mmol of the transition metal compound represented by the following formula (A) was added to this system, ethylene gas (normal pressure) was continuously introduced while 1
Prepolymerization was carried out at 0 ° C. for 2 hours. After the completion of prepolymerization, the solvent was removed by decantation, and 100 ml of hexane was used.
Was washed three times. By this operation, a prepolymerized catalyst (a) containing 3.5 mg of nickel, 180 mg of aluminum and 1.1 g of polyethylene was obtained with respect to 1 g of silica.

[0129]

Embedded image

[Polymerization] 1 liter of purified hexane was charged into a stainless steel autoclave having an internal volume of 2 liter which had been sufficiently replaced with nitrogen, 0.5 mmol of triisobutylaluminum was added, and the temperature was kept at 40 ° C. Next, to the prepolymerized catalyst (a) obtained above, 0.05 mg atom in terms of nickel atom was added, and then ethylene was introduced to start the polymerization at a total pressure of 8 kg / cm ² -G. Furthermore, ethylene was continuously supplied so that the total pressure would be 8 kg / cm ² -G, and polymerization was carried out at 40 ° C. for 1 hour.

After completion of the polymerization, the polymer slurry was filtered off,
It was dried under reduced pressure at 80 ° C. for 10 hours. Bulk density 0.40 g / c
127.3 g of m ³ polymer were obtained.

[0132]

Example 2 1 liter of purified hexane was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently purged with nitrogen, 0.5 mmol of triisobutylaluminum was added, and the temperature was kept at 40 ° C. Next, the prepolymerized catalyst (a) prepared in Example 1 was converted to 0.0 in terms of nickel atom.
After adding 3 mg atom, a mixed gas of ethylene and 1-butene (1-butene content 2.6 mol%) was introduced, and the total pressure was 8 k.
Polymerization was initiated as g / cm ² -G. Furthermore, the total pressure is 8
The above mixed gas of ethylene and 1-butene was continuously supplied so as to obtain kg / cm ² -G, and polymerization was carried out at 40 ° C. for 1 hour.

After completion of the polymerization, the polymer slurry was filtered off,
It was dried under reduced pressure at 80 ° C. for 10 hours. Bulk density 0.39g / c
101.7 g of m ³ polymer was obtained.

[0134]

Example 3 150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Then, the pressure was returned to normal pressure by introducing a mixed gas of ethylene and 1-butene (1-butene content 2.6 mol%), and the temperature in the system was adjusted to 40 ° C. Next, 0.02 mg of the prepolymerized catalyst (a) prepared in Example 1 in terms of nickel atom and 0.5 mmol of triisobutylaluminum,
After the addition to the autoclave, the mixed gas of ethylene and 1-butene was introduced, and the total pressure was set to 8 kg / cm ² -G to start the polymerization. Further, the above mixed gas of ethylene and 1-butene was continuously supplied so that the total pressure would be 8 kg / cm ² -G, and polymerization was carried out at 40 ° C. for 1 hour.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It was dried under reduced pressure at 0 ° C for 10 hours. As a result, the bulk density is 0.3
56.8 g of 7 g / cm ³ polymer was obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of a process for preparing an olefin polymerization catalyst according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Hayashi 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A fine particle carrier (A), (B) a transition metal compound of Groups 8 to 10 of the periodic table represented by the following general formula (I), and (C) (C-1) organoaluminum oxy. Compound, (C-2) alkylboronic acid derivative and (C-3) Lewis acid or at least one compound selected from ionic compounds, and optionally (D) an organometallic compound as a catalyst component and an olefin A catalyst for olefin polymerization, characterized by being prepolymerized; (In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R ¹ and R ² May be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, and m and n may be the same or different from each other, 1
Or 2 which are each a number satisfying the valences of X ¹ and X ² , and R ³ is (However, R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹ and R
⁷² may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group. ), R ⁴ and R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ ,
-SR ⁹ , -N (R ¹⁰ ) ₂ or -P (R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. And R ⁴ and R ⁵ may combine with each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ and R ⁶² ) and R ⁷ (or R ⁷¹ and R ⁷²⁾ ), Two or more of these may be linked to each other to form a ring. ) 2. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound represented by the general formula (I) is a compound represented by the following general formula (I ′); (In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R ¹ and R ² R ⁶ and R ⁷ may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, R ⁶ and R ⁷ may be the same or different and represent a hydrogen atom or a hydrocarbon group, R ⁴ and R ⁵ May be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , or
-SR ⁹ , -N (R ¹⁰ ) ₂ or -P (R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. ), R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ and R ⁷ are ring groups in which two or more of them are linked to each other. May be formed. ) 3. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.