JP2001240610A - Olefin polymerization catalyst and method for producing polyolefin using the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To efficiently produce polyolefin. SOLUTION: (A) A transition metal compound having at least one sulfoximine ligand, (B) an activation co-catalyst, and if necessary, (C) an olefin polymerization catalyst containing an organometallic compound as a constituent component are used. .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization using a transition metal compound and a method for olefin polymerization. More specifically, the present invention relates to a method for efficiently producing a polyolefin by using a transition metal compound having a specific structure as a component of an olefin polymerization catalyst.

[0002]

2. Description of the Related Art A homogeneous olefin polymerization catalyst using a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl derivative as a ligand in combination with an aluminoxane has high activity, and is useful for producing polyolefins. It is known to be useful (JP-A-58-19309). Furthermore, when such an organometallic complex having a cyclopentadienyl group is used for olefin polymerization as a component of a catalyst, the resulting polyolefin is known to be a polymer having a narrow molecular weight distribution and a uniform composition distribution. I have.

In recent years, in order to develop a more excellent catalyst for homogeneous olefin polymerization, a transition metal compound using a hetero atom other than a cyclopentadienyl ring as a ligand is used as a component of the catalyst for homogeneous olefin polymerization. Consideration is being actively given. For example, olefin polymerization catalysts using a transition metal compound having a nitrogen atom as a ligand are disclosed in JP-A-8-176217 and JP-A-8-24.
No. 5,713, discloses an olefin polymerization catalyst comprising a titanium amide compound in which a dialkylamine ligand is bonded to a titanium atom. Further, Japanese Patent Application Laid-Open
JP-298216 discloses an olefin polymerization catalyst comprising a transition metal amide compound having a cross-linkable aromatic amine compound as a ligand as a catalyst component.

[0004] Many studies using a transition metal complex having a nitrogen atom as a ligand for olefin polymerization have been conducted from an academic viewpoint. H. McConville
e et al. Am. Chem. Soc. , 118, 10
008 (1996). In [ArN (CH ₂ ) ₃ NA
r] Diamide complex represented by TiMe ₂ and B (C ₆ F ₅ ) ₃
The living polymerization of 1-hexene is carried out using a catalyst system consisting of In addition, R. R. Schrock et al.
J. Am. Chem. Soc. , 119, 3830 (1
997). At the tridentate diamine complex [(t-BuN-
_{o-C 6 H 4) 2} O] ZrMe 2 and B (C ₆ F ₅₎ using a catalyst system comprising _3, is carried out living polymerization of 1-hexene. In addition, Organometallic, 15,
562 (1996). And Organometallic
s, 17, 308 (1998). [Mes ₂ BNC
H ^₂ CH ₂ NBMes _2] ^2- bis (such as Boriruamido)
A group 4 transition metal compound was synthesized using a ligand having a structure, and it has been shown that the transition metal compound has ethylene polymerization activity.

Recently, it has been disclosed and reported that an extremely high polymerization activity is exhibited when an aldimine group 4 transition metal complex having a specific structure is used as a component of an olefin polymerization catalyst (eg, EP 874005).
No. (1998), Symposium on Polymers (1999) 48
Vol. 8, page 1676).

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an olefin polymerization catalyst capable of efficiently producing a polyolefin, and to provide a method for producing a polyolefin using the catalyst.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, used a transition metal compound having a sulfoximine ligand as a component of a catalyst for olefin polymerization, By combining a cocatalyst, a new catalyst system capable of efficiently producing polyolefin has been found, and the present invention has been completed. That is, the present invention provides a catalyst for olefin polymerization comprising a transition metal compound having a sulfoximine ligand and an activating co-catalyst as constituents.Furthermore, polymerization of olefin is performed using the olefin polymerization catalyst. And a method for producing a polyolefin.

Hereinafter, the present invention will be described in detail. The present invention is characterized in that a transition metal compound having a sulfoximine ligand is used as a component of an olefin polymerization catalyst. Although there is no limitation on the sulfoximine ligand used, the following general formula (1), (2), (3) or (4)

[0009]

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[0010]

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[0011]

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[0012]

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It is desirable to use a compound represented by the formula:

In the general formula (1), M represents a transition metal atom selected from Groups 3 to 12 of the periodic table. Xs may be the same or different, and each represents a hydrogen atom, a chlorine atom, a bromine atom,
Halogen atom such as iodine atom, methyl group, ethyl group,
Isopropyl group, tert-butyl group, hydrocarbon group having 1 to 20 carbon atoms such as benzyl group, trimethylsilyl group,
C 1-20 carbon atoms such as a silicon-containing hydrocarbon group having 1 to 20 carbon atoms such as trimethylsilylmethyl group, methoxy group, ethoxy group, isopropoxy group and tert-butoxy group;
A dialkylamino or diarylamino group having 1 to 20 carbon atoms, such as an alkoxy group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, and a dibenzylamino group. R ¹ is a methyl group,
Ethyl group, propyl group, butyl group, octyl group, isopropyl group, tert-butyl group, benzyl group, phenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, adamantyl group A hydrocarbon group having 1 to 20 carbon atoms, such as a trimethylsilyl group, a silicon-containing hydrocarbon group represented by a trimethylsilylmethyl group, or a nitrogen atom, a phosphorus atom, an oxygen atom,
And a hydrocarbon group containing a sulfur atom. When p is 2, R ¹ may combine with each other to form a ring. R ² may be the same or different, and may be a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an isopropyl group, a tert-butyl group, a benzyl group, a phenyl group,
Silicon-containing hydrocarbons represented by C1-C20 hydrocarbon groups such as 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, adamantyl group, trimethylsilyl group and trimethylsilylmethyl group And a hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2,
R ² may combine with each other to form a ring. R ^{3 to} R ⁶ are methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, benzyl, phenyl, 2,6-dimethylphenyl, 2,6
-A hydrocarbon group having 1 to 20 carbon atoms such as a diisopropylphenyl group, a mesityl group, a naphthyl group and an adamantyl group; a silicon-containing hydrocarbon group represented by a trimethylsilyl group and a trimethylsilylmethyl group. These groups may combine with each other to form a ring. Y ¹ is an amino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylamino group or a phenylamino group, and a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylphosphino group or a phenylphosphino group. A hydrocarbon group containing an element of group 15 of the periodic table, a silicon-containing hydrocarbon group containing an element of group 15 of the periodic table, or an element of group 16 of the periodic table such as an oxygen atom or a sulfur atom. A possible group. Y
Specific examples of ¹ include an oxygen atom, a sulfur atom, a methylamino group, an isopropylamino group, a tert-butylamino group, a phenylamino group, a 2,6-dimethylphenylamino group, a 2,6-diisopropylphenylamino group And the like. n represents the number of X bonded to the transition metal, and is an integer satisfying the following formula (i).

N = [oxidation number of M] -p (i) p represents the number of sulfoximine ligands in the transition metal compound, and represents 1 or 2. The transition metal compound represented by the general formula (1) may have a structure represented by the following general formula (5) depending on the preparation conditions of the complex, the type of the substituent, the state of the complex, and the like.

[0016]

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In the general formula (2), M represents a transition metal atom selected from Groups 3 to 12 of the periodic table. Xs may be the same or different, and each represents a hydrogen atom, a chlorine atom, a bromine atom,
Halogen atom such as iodine atom, methyl group, ethyl group,
Isopropyl group, tert-butyl group, hydrocarbon group having 1 to 20 carbon atoms such as benzyl group, trimethylsilyl group,
C 1-20 carbon atoms such as a silicon-containing hydrocarbon group having 1 to 20 carbon atoms such as trimethylsilylmethyl group, methoxy group, ethoxy group, isopropoxy group and tert-butoxy group;
A dialkylamino or diarylamino group having 1 to 20 carbon atoms, such as an alkoxy group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, and a dibenzylamino group. R ¹ is a methyl group,
Ethyl group, propyl group, butyl group, octyl group, isopropyl group, tert-butyl group, benzyl group, phenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, adamantyl group A hydrocarbon group having 1 to 20 carbon atoms, such as a trimethylsilyl group, a silicon-containing hydrocarbon group represented by a trimethylsilylmethyl group, or a nitrogen atom, a phosphorus atom, an oxygen atom,
And a hydrocarbon group containing a sulfur atom. When p is 2, R ¹ may combine with each other to form a ring. R ^{3 to} R
⁶ is methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, benzyl, phenyl, 2,6-dimethylphenyl, 2,
Examples thereof include a hydrocarbon group having 1 to 20 carbon atoms such as a 6-diisopropylphenyl group, a mesityl group, a naphthyl group, and an adamantyl group, and a silicon-containing hydrocarbon group represented by a trimethylsilyl group and a trimethylsilylmethyl group. These groups may combine with each other to form a ring. Y ² is an amino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylamino group or a phenylamino group; a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylphosphino group or a phenylphosphino group. A C1-20 alkoxy group such as a methoxy group or a phenoxy group, a C1-20 thioalkoxy group such as a thiomethoxy group or a thiophenoxy group, a hydrocarbon group containing a Group 15 element, and a periodic table 1.
A silicon-containing hydrocarbon group containing an element of Group V, a hydrocarbon group containing an element of Group 16 of the periodic table, or a silicon-containing hydrocarbon group containing an element of Group 16 of the periodic table; Group. Specific examples of Y ² include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a phenoxy group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, and the like. n represents an integer satisfying the following formula (i).

N = [oxidation number of M] -p (i) p represents the number of sulfoximine ligands in the transition metal compound, and represents 1 or 2.

In the general formula (3), M represents a transition metal atom selected from Groups 3 to 12 of the periodic table. Xs may be the same or different, and each represents a hydrogen atom, a chlorine atom, a bromine atom,
Halogen atom such as iodine atom, methyl group, ethyl group,
Isopropyl group, tert-butyl group, hydrocarbon group having 1 to 20 carbon atoms such as benzyl group, trimethylsilyl group,
C 1-20 carbon atoms such as a silicon-containing hydrocarbon group having 1 to 20 carbon atoms such as trimethylsilylmethyl group, methoxy group, ethoxy group, isopropoxy group and tert-butoxy group;
A dialkylamino or diarylamino group having 1 to 20 carbon atoms, such as an alkoxy group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, and a dibenzylamino group. R ¹ is a methyl group,
Ethyl group, propyl group, butyl group, octyl group, isopropyl group, tert-butyl group, benzyl group, phenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, adamantyl group A hydrocarbon group having 1 to 20 carbon atoms, such as a trimethylsilyl group, a silicon-containing hydrocarbon group represented by a trimethylsilylmethyl group, or a nitrogen atom, a phosphorus atom, an oxygen atom,
And a hydrocarbon group containing a sulfur atom. R ^{3 to} R ⁶ are methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, benzyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl And a hydrocarbon group having 1 to 20 carbon atoms, such as a mesityl group, a naphthyl group, and an adamantyl group, and a silicon-containing hydrocarbon group represented by a trimethylsilyl group and a trimethylsilylmethyl group. These groups may combine with each other to form a ring. Y ¹ is an amino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylamino group or a phenylamino group, and a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylphosphino group or a phenylphosphino group. A hydrocarbon group containing an element of group 15 of the periodic table, a silicon-containing hydrocarbon group containing an element of group 15 of the periodic table, or an element of group 16 of the periodic table such as an oxygen atom or a sulfur atom. Shows possible groups. Specific examples of Y ¹ include an oxygen atom, a sulfur atom, a methylamino group, an isopropylamino group, a tert-butylamino group, a phenylamino group, a 2,6-dimethylphenylamino group, and a 2,6-diisopropylphenylamino And the like. m represents the number of X bonded to the transition metal, and is an integer satisfying the following formula (ii).

M = [oxidation number of M] -2 (ii) In the general formula (4), M represents a transition metal atom selected from Groups 3 to 12 of the periodic table. Xs may be the same or different from each other, and include a halogen atom such as a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom;
A silicon-containing hydrocarbon group having 1 to 20 carbon atoms, such as 20 hydrocarbon groups, trimethylsilyl group, trimethylsilylmethyl group, methoxy group, ethoxy group, isopropoxy group, t
an alkoxy group having 1 to 20 carbon atoms such as ert-butoxy group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, a dialkylamino group having 1 to 20 carbon atoms such as a dibenzylamino group or a diarylamino group; Show. R ¹ is methyl, ethyl, propyl, butyl, octyl, isopropyl, te
rt-butyl group, benzyl group, phenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, hydrocarbon group having 1 to 20 carbon atoms such as adamantyl group, trimethylsilyl group, A silicon-containing hydrocarbon group represented by a trimethylsilylmethyl group, a hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, and the like are shown. When p is 2, R ¹ may combine with each other to form a ring. R ² may be the same or different, and may be a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an isopropyl group, a tert group.
1-carbon group such as butyl group, benzyl group, phenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, adamantyl group, etc.
-20, a silicon-containing hydrocarbon group represented by a trimethylsilyl group, a trimethylsilylmethyl group, or a hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2, R ² may combine with each other to form a ring. R ^{3 to} R ⁶ are methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, benzyl, phenyl,
Silicon-containing hydrocarbons represented by C1-C20 hydrocarbon groups such as 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, naphthyl group, adamantyl group, trimethylsilyl group and trimethylsilylmethyl group And the like. These groups may combine with each other to form a ring. Y ² is an amino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylamino group or a phenylamino group; a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms such as a methylphosphino group or a phenylphosphino group. A C1-C20 alkoxy group such as a methoxy group or a phenoxy group, a C1-C20 thioalkoxy group such as a thiomethoxy group or a thiophenoxy group, a hydrocarbon group containing a Group 15 element, a periodic table 15 A silicon-containing hydrocarbon group containing a group 16 element, a hydrocarbon group containing a group 16 element in the periodic table, or a silicon-containing hydrocarbon group containing an element in the periodic table 16; Is shown. Specific examples of Y ² include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a phenoxy group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, and the like. r shows the same integer as the oxidation number of M. p represents the number of sulfoximine ligands in the transition metal compound, and represents 1 or 2. The transition metal compound represented by the general formula (4) may have a structure represented by the following general formula (6) depending on the preparation conditions of the complex, the type of the substituent, the state of the complex, and the like.

[0021]

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As a method for synthesizing the transition metal compound having a sulfoximine ligand of the present invention, there is a method of synthesizing a corresponding sulfoxyimine ligand and then synthesizing a complex using the ligand. One method for synthesizing the corresponding sulfoximine ligands is Tetrahed
ron Letters, 1995, 36, 162
As described on page 5, there can be mentioned a method of synthesizing a sulfoxide by oxidizing a sulfide and then using o-mesitylenesulfonylhydroxylamine. Also, after sulfide is oxidized to synthesize sulfoxide, the Journal of the Ame
rican Chemical Society, 19
After synthesizing N- (p-toluenesulfonyl) sulfoximine by the method described in 1970, Vol. 92, p. 7369, a method of synthesizing the corresponding sulfoximine ligand by performing sulfuric acid treatment, and the like. However, the present invention is not limited to these methods. As a method for synthesizing the N-arylsulfoximine ligand, T
etrahedron Letters, 1998,
39, p. 5731.

As a method for synthesizing a transition metal compound having a sulfoximine ligand, a method used in an existing complex synthesis reaction can be used as it is. For example,
In a complex having a covalent bond with a sulfoximine ligand, such as a complex represented by the general formulas (1), (2), and (3), the sulfoximine ligand is complexed and then reacted with a transition metal compound. The corresponding complex is synthesized by performing a transmetalation reaction, or by reacting a sulfoximine ligand with a transition metal amide complex or a transition metal alkyl complex, and then performing a deamine reaction or a dealkane reaction. It is possible. In the case of a complex having only a sulfoximine ligand and a coordination bond, such as a complex represented by the general formula (4), a corresponding complex is synthesized by reacting the sulfoximine ligand with a transition metal compound in a reaction solvent. It is possible, but not limited to these methods. For example, in the case of a nickel complex,
Organometallics, 1998, 17
Vol., Pages 3149-3151 can be used.

As a specific example of synthesis, as shown in the formula (7), after sulfide is oxidized to sulfoxide,
N- (p-toluenesulfonyl) using tosyl azide
After synthesizing the sulfoximine, treating with sulfuric acid, the corresponding sulfoximine ligand can be synthesized. The corresponding sulfoxyimine complex can be synthesized by causing a transition metal compound to act on the corresponding sulfoximine ligand.

[0025]

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Specific examples of the transition metal compound having a sulfoximine ligand of the present invention include, but are not limited to, the following transition metal complexes.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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The (B) activating cocatalyst, which is one of the components of the catalyst for olefin polymerization in the present invention, refers to the action or reaction of the transition metal compound or the reaction product of the transition metal compound and the organometallic compound. In this case, a compound having a role of forming a polymerization active species capable of polymerizing an olefin is shown. An activation co-catalyst is a compound that forms a polymerization active species, then provides a compound that weakly coordinates or interacts with the generated polymerization active species, but does not directly react with the active species. Examples of the activating co-catalyst include alkylaluminoxane, which is widely used as a co-catalyst component of a homogeneous olefin polymerization catalyst system in recent years, an ionized ionic compound having a non-coordinating anion, and a modified clay compound. However, the present invention is not limited to these.

For example, when the activating co-catalyst is aluminoxane, its structure is represented by the following general formula (8) and / or (9)

[0034]

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(Wherein R ⁷ may be the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, a propyl group,
It is a hydrocarbon group having 1 to 20 carbon atoms such as a tert-butyl group. Q is an integer of 2 to 60. ) Is desirable. The aluminoxane may contain a small amount of an organometallic compound.

The alkylaluminoxane represented by the general formula (8) and / or (9) can be used for both the (B) activating cocatalyst and the (C) organometallic compound.

When the activating cocatalyst is an ionized ionic compound having a non-coordinating anion, its structure is a protonic acid represented by the following general formula (10),
And a compound having a structure of any of a Lewis acid represented by the general formula (12) or a Lewis acidic compound represented by the general formula (13).

[HL ¹ ] [B (Ar) ₄ ] (10) [AL ² _s ] [B (Ar) ₄ ] (11) [D] [B (Ar) ₄ ] (12) B (Ar) ₃ (13) (where H is a proton, B is a boron atom or an aluminum atom, L ¹ is a Lewis base, L ² is a Lewis base or a cyclopentadienyl group. A is lithium, iron or silver. A cation of a metal selected from
D is a carbonium cation or a tropylium cation. Ar is a halogen-substituted aryl group having 6 to 20 carbon atoms. s is an integer of 0 to 2. As specific examples of the protonic acid represented by the general formula (10),
Diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) borate, hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium Tetrakis (pentafluorophenyl) borate, tri-N-butylammoniumtetrakis (pentafluorophenyl)
Borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate,
Tetramethyleneoxonium tetrakis (pentafluorophenyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) aluminate, tri-n-butylammonium tetrakis (pentafluorophenyl) A) aluminates and the like, but are not limited to these.

Specific examples of the ionized ionic compound represented by the general formula (11) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, and ether complexes thereof. , Ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) borate and ferrocenium tetrakis (pentafluorophenyl) aluminate, and silver such as silver tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) aluminate Examples of the salt include, but are not limited to, salts.

As the Lewis acid represented by the general formula (12), specifically, trityltetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, Examples include, but are not limited to, tropylium tetrakis (pentafluorophenyl) aluminate.

Specific examples of the Lewis acidic compound represented by the general formula (13) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2 3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum, etc. Examples include, but are not limited to:

When a coordinating compound such as phosphine is coordinated with the transition metal compound having a sulfoximine ligand of the present invention, a zero-valent transition metal compound or diborane, borane. Lewis acids such as complexes can be used. Examples of the zero-valent transition metal compound include bis (1,5-cyclooctadiene) nickel and bis (1,5-cyclooctadiene) palladium.

When the activating cocatalyst which is a component of the olefin polymerization catalyst of the present invention is a modified clay compound, the clay compound used preferably has a cation exchange ability. Further, the clay compound used in the present invention,
Acid, alkali treatment, salt treatment and organic compounds,
It is preferable to perform a chemical treatment such as a complex formation by an inorganic compound treatment.

As the clay compound, naturally occurring kaolinites such as kaolinite, dickite and halloysite, montmorillonite, hectorite, beidellite,
Smectites such as saponite, teniolite and sauconite; mica such as muscovite, paragonite and illite;
Vermiculite group, margarite, brittle mica group such as clintonite, dombasite, coucheite, curbstone group such as clinochlore, sepiolite, palygorskite and the like, and artificially synthesized clay compounds can be mentioned, but are not limited thereto. .

Examples of the acid used for the chemical treatment include Bronsted acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. As the alkali, sodium hydroxide, potassium hydroxide and calcium hydroxide are preferably used. Compounds used in the salt treatment include ionic halides such as sodium chloride, potassium chloride, lithium chloride, magnesium chloride, aluminum chloride, iron chloride, and ammonium chloride; sulfides such as sodium sulfate, potassium sulfate, aluminum sulfate, and ammonium sulfate. Carbonates such as potassium carbonate, sodium carbonate, and calcium carbonate; inorganic salts such as sodium phosphate, potassium phosphate, aluminum phosphate, and ammonium phosphate; and sodium acetate, potassium acetate, potassium oxalate, and citrate. Organic acid salts such as sodium acid salt and sodium tartrate can be exemplified.

Examples of the organic compound used to form the organic complex of the clay compound include onium salts, compounds that form carbon cations such as trityl chloride and tropylium bromide, and complexes that form metal complex cations such as ferrocenium salts. Compounds are exemplified. Aluminum hydroxide as the inorganic compound used to form the inorganic composite,
Metal hydroxides that generate hydroxide cations such as zirconium hydroxide and chromium hydroxide can be exemplified.

Among the modified clay compounds used in the present invention, a modified clay compound-organic ion complex in which a metal ion which is an exchangeable cation present in the clay compound is replaced with a specific organic cation component is particularly preferred. It is a clay compound. Specific examples of the organic cation to be introduced into the modified clay compound include aliphatic ammonium cations such as butyl ammonium, hexyl ammonium, decyl ammonium, dodecyl ammonium, diamyl ammonium, tributyl ammonium, N, N-dimethyldecylammonium, and anilinium. , N-methylanilinium, N, N-dimethylanilinium, N-ethylanilinium, N, N-diethylanilinium, benzylammonium, toluidinium, dibenzylammonium, tribenzylammonium, N, N, 2,4, 6
Examples thereof include ammonium ions such as aromatic ammonium cations such as pentamethylanilinium, and oxonium ions such as dimethyloxonium and diethyloxonium, but are not limited thereto.

As a component of the olefin polymerization catalyst of the present invention, an organometallic compound (C) can be used together with a transition metal compound and an activating cocatalyst. The organic metal compound is preferably a compound capable of inactivating a catalyst poison component present in the polymerization system, and at the same time, capable of forming an alkyl form of a transition metal compound.
Specifically, methyl lithium, alkyl lithium compounds such as n-butyl lithium, methyl magnesium chloride, ethyl magnesium chloride, isopropyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, isopropyl magnesium bromide,
Grignard reagents such as benzylmagnesium bromide, dialkylmagnesiums such as dimethylmagnesium, dialkylzincs such as dimethylzinc and diethylzinc, alkylboranes such as trimethylborane and triethylborane, alkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum, methyl Alkyl aluminoxanes such as aluminoxane, butylaluminoxane, tert-butylaluminoxane and the like can be mentioned. Preferable examples of the organometallic compound include an organoaluminum compound represented by the following general formula (14) (R ⁸ ) ₃ Al (14) (wherein R ⁸ may be the same or different, and a hydrogen atom, an amide group , Represents an alkoxy group, a hydrocarbon group,
At least one of them is a hydrocarbon group. ) And alkylaluminoxanes.

More preferred compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum and the like. The catalyst for olefin polymerization in the present invention comprises the components (A) and (B),
Alternatively, the component (A), the component (B), and the component (C) are used as constituents, and if necessary, a solid catalyst supported on a fine particle carrier (D) is used together with the organic aluminum compound (E). Thus, it can be used as an olefin polymerization catalyst. If necessary, the supported olefin polymerization catalyst may be used as an olefin polymerization catalyst by using a solid catalyst obtained by prepolymerizing (F) an olefin together with (G) an organoaluminum compound. is there. As described above, when a polyolefin is produced in the presence of a solid catalyst component, the obtained polyolefin has a high bulk density, does not cause adhesion of the polyolefin to a reactor wall, and is particularly stable in a gas phase polymerization or a slurry polymerization. Manufacturing can be realized.

The (D) fine particle carrier used as a component of the above-mentioned solid catalyst is preferably an inorganic carrier or an organic carrier.
₂ , Al ₂ O ₃ , ZrO, B ₂ O ₃ , CaO, ZnO, Mg
Cl ₂ , CaCl ₂ and combinations thereof, and organic carriers such as polyethylene, polypropylene, poly (1-
Butenes), polyolefins such as polystyrene, and mixtures of these polyolefins with polar polymers such as polyethyl methacrylate, polyester, and polyimide; copolymers of organic carriers; and combinations of these. Although the shape of these fine particle carriers is not limited, it is preferable that the particle diameter is 5 μm to 200 μm.

In the catalyst for olefin polymerization in the present invention, (D) an organoaluminum compound used together with a solid catalyst supported on a fine particle carrier includes a compound represented by the following general formula (15).

(R ⁹ ) ₃ Al (15) (wherein R ⁹ may be the same or different and represents a hydrogen atom, an amide group, an alkoxide group, or a hydrocarbon group, at least one of which is a hydrocarbon group) Examples of such a compound include trimethylaluminum, triethylaluminum, triisobutylaluminum and the like.

The (F) olefin used in the prepolymerization of the above-mentioned solid catalyst is not limited, but may have 2 to 16 carbon atoms.
Α-olefin or cyclic olefin is preferred, and specifically, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,
Α-olefins such as octene; and cyclic olefins such as norbornene and norbornadiene. These may be used alone or as a mixture of two or more. When pre-polymerization is carried out using two or more olefins, the pre-polymerization can be carried out sequentially or simultaneously by adding them to the reaction system.

The method of performing the prepolymerization is not particularly limited as long as the solid catalyst for olefin polymerization and the olefin (F) can be polymerized. Generally, -50 to 10
0 ° C, preferably -20 to 60 ° C, more preferably -1.
In a temperature range of 0 to 40 ° C., it can be carried out under normal pressure or under pressure, under a flowing condition when processing in a gas phase, under a stirring condition when processing in a liquid phase, Preferably, sufficient contact is made.

(G) for use with a pre-polymerized solid catalyst
As the organic aluminum compound, the following general formula (16)
Can be mentioned.

(R ¹⁰ ) ₃ Al (16) (wherein R ¹⁰ may be the same or different and represents a hydrogen atom, an amide group, an alkoxide group, or a hydrocarbon group, at least one of which is a hydrocarbon Examples of such a compound include trimethylaluminum, triethylaluminum, triisobutylaluminum and the like.

The ratio of the component (A), the component (B) and the component (C) in the present invention is not limited, but is preferably (B).
When the components are represented by the general formulas (8) and / or (9), the molar ratio of the components (A) and (C) per metal atom is (A component) :( C component) = 100: 1 to 1 1: 1000
00, particularly preferably in the range of 1: 1 to 1: 10000, and the ratio of the component (A) to the component (B) is (A component) :( B component) = 100: 1 to 1: 10,000
00, and particularly preferably in the range of 1: 1 to 1: 100,000. The component (B) has the general formula (10) or (1)
When represented by the compound represented by (1), (12) or (13), the molar ratio of the (A) component to the (C) component per metal atom is (A component) :( C component) = 100: 1-1: 1
00000, especially 1: 1 to 1: 10000
The ratio of the component (A) to the component (B) is preferably (A component) :( B component) = 10: 1 to 1: 100.
0, and particularly preferably in the range of 3: 1 to 1: 100. When the component (B) is a modified clay compound,
The molar ratio of component (A) to component (C) per metal atom is (component A) :( component C) = 100: 1 to 1: 10000
0, particularly preferably in the range of 1: 1 to 1: 10000, and the ratio of component (A) to component (B) is (A component) :( B component) = 10: 1 to 1: It is preferably in the range of 3: 1 to 1: 1000.

The method for preparing the olefin polymerization catalyst comprising the components (A), (B) and (C) is not limited, and the preparation may be carried out in an inert solvent for each component or in a monomer to be polymerized. Can be used as a solvent and a method of mixing. Further, there is no restriction on the order in which these components are reacted, and there is no restriction on the temperature or the processing time for performing this processing. Further, it is also possible to prepare an olefin polymerization catalyst by using two or more kinds of each component.

The amount of the (D) fine particle carrier and (F) olefin that can be used as required in the present invention is not limited, and any amount can be used as long as a solid catalyst can be formed. Furthermore, there is no particular limitation on the amount of the (A) organoaluminum compound and (G) the organoaluminum compound used together with the solid catalyst. Furthermore, there is no limitation on the method of preparing the solid catalyst, the order in which the components are reacted or acted on, and there is no limitation on the temperature or time for the treatment.

The catalyst in the present invention can be prepared by a usual polymerization method,
That is, it can be used for any of slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization and bulk polymerization. In the present invention, the polymerization means not only homopolymerization but also copolymerization, and the polyolefin obtained by these polymerizations is used in a meaning including not only a homopolymer but also a copolymer.

The olefin polymerization in the present invention can be carried out in a gas phase or a liquid phase. In particular, when it is carried out in a gas phase, it is possible to efficiently and stably produce an olefin polymer having a uniform particle shape. it can. When the polymerization is performed in the liquid phase, the solvent used may be any organic solvent generally used, and specifically, benzene, toluene,
Xylene, pentane, hexane, heptane and the like can be mentioned, and olefin itself such as propylene, 1-butene, 1-octene and 1-hexene can be used as a solvent.

In the present invention, the olefin used for the polymerization is ethylene, propylene, 1-butene, 4-methyl-
Α-olefins such as 1-pentene, 1-hexene, 1-octene, styrene and styrene derivatives, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4
-Conjugated and non-conjugated dienes such as -hexadiene and 7-methyl-1,6-octadiene; cyclic olefins such as cyclobutene; and polar vinyl monomers having a carbonyl group such as acrylic acid, methyl acrylate, butyl acrylate and vinyl acetate. And ethylene and propylene,
Two or more kinds of components such as ethylene and methyl acrylate, ethylene and 1-hexene and styrene, and ethylene and propylene and ethylidene norbornene can be mixed and polymerized.

In producing a polyolefin using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration are not particularly limited, but the polymerization temperature is -100 to 300 ° C. For 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. The polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system, and can be carried out in two or more stages by changing the polymerization conditions. Further, the polyolefin obtained after the completion of the polymerization can be separated and recovered from the polymerization solvent by a conventionally known method, and can be obtained by drying.

[0064]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The transition metal compound was synthesized using a Schlenk technique or a dry box, and all operations were performed in an argon or nitrogen atmosphere. The solvents used for the preparation of the transition metal compounds were all deoxygenated and dehydrated by known methods. The polymerization reaction was carried out at a predetermined temperature for a predetermined time while continuously supplying ethylene gas using a 2 l autoclave. The solvent used for the polymerization was deoxygenated and dehydrated by a known method. As the ethylene gas, a polymerization grade was used as it was.

Example 1 [Sulfoximine complex A: bis [2- (S-methyl-
N-phenyl-sulfoxyimino) phenoxy] synthesis of zirconium dichloride]

[0067]

Embedded image

2- (S-methyl-N) cooled to -78 ° C
-Phenyl-sulfoximino) phenol (2.47
g, 10 mmol) in a THF solution (100 ml).
-BuLi hexane solution (1.50 mol / l, 7.
3 ml, 11 mmol) were added slowly. 3 as it is
After stirring for 0 minutes, the temperature was raised to room temperature, and the mixture was further stirred overnight. After the completion of the reaction, the solvent was distilled off under reduced pressure, toluene (70 ml) was added, and the mixture was cooled to -78 ° C.
₄ A toluene suspension (30 ml) of 1.17 g (5.0 mmol) was slowly added. After stirring for 1 hour as it was, the temperature was slowly raised to room temperature, and further stirred at room temperature overnight. After completion of the reaction, the reaction mixture was filtered, the filtrate was concentrated, and left at −30 ° C. overnight. The precipitated solid was collected by filtration to obtain sulfoximine complex A: bis [2- (S-
Methyl-N-phenyl-sulfoxyimino) phenoxy] zirconium dichloride was obtained (1.02 g,
1.6 mmol, yield 32%).

[Preparation of Catalyst Solution] In a 1-liter Schlenk flask, toluene (500 ml), methylaluminoxane (PMAO, manufactured by Tosoh Akzo Co., Ltd., 10 mmol in terms of aluminum atom), and toluene of sulfoxyimine complex A prepared by the above method were used. A solution (10 μmol in terms of zirconium) was added, and the mixture was stirred at room temperature for 10 minutes.

[Ethylene polymerization] A catalyst solution prepared by the above method was added to a 2 liter autoclave. 8 kg / cm ² G while maintaining the temperature inside the autoclave at 80 ° C.
The polymerization was carried out at 80 ° C. for 1 hour while continuously supplying ethylene so as to obtain an ethylene pressure of 11 g, thereby obtaining 11 g of a polymer.

Example 2 [Sulfoximine complex B: [2- {S-methyl-N-
Synthesis of (2,6-dimethylphenyl) sulfoximino diphenoxy] (triphenylphosphine) (phenyl) nickel]

[0072]

Embedded image

Sodium hydride (60% concentration product 4 in mineral oil)
3 mg, 1.1 mmol) and 2- {S-methyl-N-
(2,6-Dimethylphenyl) sulfoximino diphenol (116 mg, 0.42 mmol) in THF
Stirred at room temperature for 1 hour. The THF insolubles were removed and the filtrate was concentrated under reduced pressure to give a white solid. The solid was washed with pentane and dried under reduced pressure. After adding 7 ml of benzene and cooling with ice, NiCl (Ph) (PP
_{h 3) 2 (219mg, 0.31mmol} ) was added.
After stirring at room temperature for 6 hours, the mixture was filtered, and the filtrate was added to about 1/5 of the total volume.
And concentrated to. When 30 ml of pentane was added thereto, a yellow solid precipitated. The solid was collected by filtration, washed with pentane, and dried under vacuum to obtain 285 mg of a solid. This was purified by recrystallization from hexane / benzene = 4/1.

[Preparation of Catalyst Solution] In a 500 ml Schlenk flask, the nickel complex (90 μm) obtained above was placed.
mol), bis (1,5-cyclooctadiene) nickel (57 mg, 207 μmol) and toluene (50
0 ml) and stirred at room temperature for 5 minutes.

[Ethylene Polymerization] The catalyst solution prepared by the above method was added to a 2-liter autoclave. While keeping the temperature inside the autoclave at 40 ° C., 6 kg / cm ² G
The polymerization was carried out at 40 ° C. for 1 hour while continuously supplying ethylene so that the ethylene pressure became 1.5 g, to obtain 1.5 g of a polymer.

[0076]

The olefin polymerization catalyst comprising a transition metal compound having at least one sulfoximine ligand according to the present invention is extremely effective for olefin polymerization, and this catalyst is used as an olefin polymerization catalyst. This makes it possible to efficiently produce polyolefin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference)

Claims (7)

[Claims] An olefin polymerization catalyst comprising (A) a transition metal compound having at least one sulfoximine ligand and (B) an activation promoter. 2. An olefin polymerization catalyst comprising (A) a transition metal compound having at least one sulfoximine ligand, (B) an activating co-catalyst and (C) an organometallic compound. 3. The transition metal compound having a sulfoximine ligand (A) is represented by the following general formula (1): ## STR1 ## (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 1 to 2 carbon atoms
An amino group having 0 hydrocarbon groups or 1 to 30 carbon atoms
A phosphino group having a hydrocarbon group. R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2, R ¹ may combine with each other to form a ring. R ² represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2, R ²
May combine with each other to form a ring. R ^{3 to} R ⁶ may be the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. Further, they may combine with each other to form a ring. Y ¹ includes an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon having 1 to 20 carbon atoms, a hydrocarbon group containing an element of group 15 of the periodic table, and an element of group 15 of the periodic table It represents a silicon-containing hydrocarbon group or an element belonging to Group 16 of the periodic table, and is a group capable of forming a covalent bond with the transition metal M. n represents an integer satisfying the following formula (i). n = [oxidation number of M] -p (i) p represents 1 or 2. 3. The catalyst for olefin polymerization according to claim 1, which is a compound represented by the formula: 4. The transition metal compound having a sulfoximine ligand (A) is represented by the following general formula (2): (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 1 to 2 carbon atoms
An amino group having 0 hydrocarbon groups or 1 to 30 carbon atoms
A phosphino group having a hydrocarbon group. R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2, R ¹ may combine with each other to form a ring. R ^{3 to} R ⁶ may be the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. Further, they may combine with each other to form a ring. Y ² is an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, A hydrocarbon group containing a Group 15 element of the periodic table, a silicon-containing hydrocarbon group containing a Group 15 element of the periodic table,
A hydrocarbon group containing an element of group 16 of the periodic table or the periodic table 16
It represents a silicon-containing hydrocarbon group containing a group III element and is a group capable of coordinating with a transition metal M. n represents an integer satisfying the following formula (i). n = [oxidation number of M] -p (i) p represents 1 or 2. 3. The catalyst for olefin polymerization according to claim 1, which is a compound represented by the formula: 5. The transition metal compound having a sulfoximine ligand (A) is represented by the following general formula (3): (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 1 to 2 carbon atoms
An amino group having 0 hydrocarbon groups or 1 to 30 carbon atoms
A phosphino group having a hydrocarbon group. R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. R ^{3 to} R ⁶ may be the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. Further, they may combine with each other to form a ring. Y ¹ represents an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing an element belonging to Group 15 of the periodic table, or an element belonging to Group 15 of the periodic table. And a group capable of forming a covalent bond with a transition metal M. m represents an integer satisfying the following formula (ii). 3. The catalyst for olefin polymerization according to claim 1, wherein m is a compound represented by the following formula: m = [oxidation number of M] -2 (ii). 6. The transition metal compound (A) having a sulfoximine ligand is represented by the following general formula (4): (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 1 to 2 carbon atoms
An amino group having 0 hydrocarbon groups or 1 to 30 carbon atoms
A phosphino group having a hydrocarbon group. R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2, R ¹ may combine with each other to form a ring. R ² represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. When p is 2, R ²
May combine with each other to form a ring. R ^{3 to} R ⁶ may be the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. Further, they may combine with each other to form a ring. Y ² is an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, Periodic Table 15
A hydrocarbon group containing an element of group 16 of the periodic table, a silicon-containing hydrocarbon group containing an element of group 15 of the periodic table, a hydrocarbon group containing an element of group 16 of the periodic table, or a silicon-containing hydrocarbon group containing an element of group 16 of the periodic table. A group capable of coordinating with the transition metal M.
r shows the same integer as the oxidation number of M. p represents 1 or 2. 3. The catalyst for olefin polymerization according to claim 1, which is a compound represented by the formula: 7. A method for producing a polyolefin, comprising polymerizing an olefin using the olefin polymerization catalyst according to claim 1.